TW202035367A - Polymer and use thereof - Google Patents

Polymer and use thereof Download PDF

Info

Publication number
TW202035367A
TW202035367A TW108134987A TW108134987A TW202035367A TW 202035367 A TW202035367 A TW 202035367A TW 108134987 A TW108134987 A TW 108134987A TW 108134987 A TW108134987 A TW 108134987A TW 202035367 A TW202035367 A TW 202035367A
Authority
TW
Taiwan
Prior art keywords
group
carbons
charge
transporting
polymer
Prior art date
Application number
TW108134987A
Other languages
Chinese (zh)
Other versions
TWI837184B (en
Inventor
中澤太一
中家直樹
Original Assignee
日商日產化學股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商日產化學股份有限公司 filed Critical 日商日產化學股份有限公司
Publication of TW202035367A publication Critical patent/TW202035367A/en
Application granted granted Critical
Publication of TWI837184B publication Critical patent/TWI837184B/en

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F26/12—N-Vinyl-carbazole
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Abstract

Provided is a polymer which exhibits good charge transport properties when fired at a low temperature, gives a thin film having a high refractive index and high transparency, and can realize an organic EL element having excellent characteristics when this thin film is used in a hole injection layer or the like. For example, the polymer contains a repeating unit represented by a formula.

Description

聚合物及其用途Polymers and their uses

本發明係關於聚合物及其用途。The present invention relates to polymers and their uses.

有機電致發光(EL)元件中，作為發光層或電荷注入層，使用有機化合物所構成的電荷輸送性薄膜。尤其，電洞注入層負責陽極與電洞輸送層或發光層之電荷授受，具有用以達成有機EL元件的低電壓驅動及高亮度的重要機能。In an organic electroluminescence (EL) element, a charge-transporting film composed of an organic compound is used as a light-emitting layer or a charge injection layer. In particular, the hole injection layer is responsible for the charge transfer between the anode and the hole transport layer or the light emitting layer, and has an important function for achieving low voltage driving and high brightness of the organic EL device.

電洞注入層的形成方法大致分為蒸鍍法為代表的乾製程與旋轉塗佈法為代表的濕製程。若比較此等之製程，濕製程可大面積有效率地製造平坦性高的薄膜。因此，在有機EL顯示器大面積化不斷進展的現在，期待可以濕製程形成之電洞注入層。The method of forming the hole injection layer is roughly divided into a dry process represented by an evaporation method and a wet process represented by a spin coating method. Comparing these processes, the wet process can efficiently produce thin films with high flatness over a large area. Therefore, as the large-area organic EL display continues to advance, a hole injection layer that can be formed by a wet process is expected.

有鑑於如此之情況，本發明者們開發著賦予可適用各種濕製程，同時適用於有機EL元件之電洞注入層時，可實現優異的EL元件特性的薄膜之電荷輸送性材料或對用於其之有機溶劑之溶解性良好的化合物(專利文獻1～3作為參考)。In view of this situation, the inventors of the present invention have developed charge-transporting materials that can be applied to a variety of wet processes, while being applied to the hole injection layer of organic EL devices, and can achieve excellent EL device characteristics. The compound has good solubility in organic solvents (Patent Documents 1 to 3 are for reference).

另一方面，到目前為止，為了使有機EL元件高性能化，已經做了很多努力，但是在提升光取出效率等之目的，進行調整所使用之機能膜的折射率之努力。具體上，考量元件的全體構成或鄰接之其他構件的折射率，藉由使用相對高的、或者低的折射率之電洞注入層或電洞輸送層，嘗試元件之高效率化(專利文獻4、5)。這樣，認為折射率係有機EL元件的設計上重要的要素，且在有機EL元件用材料，折射率亦為應考慮之重要的物性值。 [先前技術文獻] [專利文獻]On the other hand, many efforts have been made to improve the performance of organic EL devices. However, for the purpose of improving light extraction efficiency, efforts have been made to adjust the refractive index of the functional film used. Specifically, considering the overall configuration of the device or the refractive index of other adjacent components, by using a hole injection layer or a hole transport layer with a relatively high or low refractive index, an attempt is made to increase the efficiency of the device (Patent Document 4 , 5). In this way, the refractive index is considered to be an important element in the design of the organic EL element, and in the material for the organic EL element, the refractive index is also an important physical property value that should be considered. [Prior Technical Literature] [Patent Literature]

[專利文獻1]國際公開第2008/129947號 [專利文獻2]國際公開第2015/050253號 [專利文獻3]國際公開第2017/217457號 [專利文獻4]特表2007-536718號公報 [專利文獻5]特表2017-501585號公報[Patent Document 1] International Publication No. 2008/129947 [Patent Document 2] International Publication No. 2015/050253 [Patent Document 3] International Publication No. 2017/217457 [Patent Document 4] Special Form 2007-536718 Publication [Patent Document 5] JP 2017-501585 Publication

[發明所欲解決之課題][The problem to be solved by the invention]

本發明，考慮到上述情況，以提供低溫燒成得到電荷輸送性良好，高折射率且高透明性的薄膜，且將該薄膜用於電洞注入層等時，可實現具有優異特性的有機EL元件的聚合物為目的。 [用以解決課題之手段]The present invention takes into consideration the above circumstances to provide a low-temperature firing to obtain a thin film with good charge transportability, high refractive index and high transparency, and when the thin film is used in a hole injection layer, etc., an organic EL with excellent characteristics can be realized The polymer of the element is the purpose. [Means to solve the problem]

本發明者們，為了達到上述目的努力檢討之結果，發現包含側鏈含有具有三芳基胺構造的咔唑基之乙烯基系聚合物的電荷輸送性塗漆即使在200℃以下之低溫燒成之情況，仍得到顯示優異的電荷輸送性，且高透明性及高折射率之薄膜，將該薄膜用於電洞注入層等時，得到具有優異特性的有機EL元件，完成本發明。The inventors of the present invention have worked hard to achieve the above-mentioned objective and found that a charge-transporting paint containing a vinyl polymer containing a carbazole group with a triarylamine structure in the side chain can be fired at a low temperature below 200°C. In this case, a thin film showing excellent charge transport properties, high transparency and high refractive index is still obtained. When the thin film is used for a hole injection layer or the like, an organic EL device with excellent characteristics is obtained, and the present invention is completed.

因此，本發明提供下述聚合物及其用途。 1.一種含有下述式(1)所表示之重複單位的聚合物。

Figure 02_image001
(式中，RA 為氫原子或甲基。X為單鍵或亞甲基。R1 ～R11 各自獨立，為氫原子、鹵素原子、硝基或者氰基、或可被鹵素原子、硝基或者氰基取代的碳數1～20的烷基、碳數1～20的烷氧基、碳數6～20的芳基、碳數6～20的芳基氧基、碳數2～20的雜芳基或者碳數2～20的雜芳基氧基。ArT 為經二(碳數6～20的芳基)胺基取代的苯基。m為0～2的整數。) 2.如1的聚合物，其中，X為單鍵。 3.如1或2的聚合物，其中，R1 ～R11 為氫原子。 4.如1～3中任一的聚合物，其中，前述ArT 為p-(二苯基胺基)苯基、p-(1-萘基苯基胺基)苯基、p-[二(1-萘基)胺基]苯基、p-(1-萘基-2-萘基胺基)苯基、p-[二(2-萘基)胺基]苯基。 5.如1～4中任一的聚合物，其中，m為0或1。 6.一種電荷輸送性塗漆，其係包含(A)含有如1～5中任一的聚合物的電荷輸送性物質、及(B)有機溶劑。 7.如6的電荷輸送性塗漆，其中，進一步含有(C)摻雜劑。 8.如7的電荷輸送性塗漆，其中，前述有機溶劑含有低極性有機溶劑。 9.一種由如6～8中任一的電荷輸送性塗漆所得到的電荷輸送性薄膜。 10.一種有機電致發光元件，其係具備如9的電荷輸送性薄膜。 11.如10的有機電致發光元件，其中，前述電荷輸送性薄膜為電洞注入層或電洞輸送層。 12.一種下述式(1’)所表示之單體。
Figure 02_image003
(式中，RA 、X、R1 ～R11 、ArT 及m同前述。) [發明之效果]Therefore, the present invention provides the following polymers and their uses. 1. A polymer containing a repeating unit represented by the following formula (1).
Figure 02_image001
(In the formula, R A is a hydrogen atom or a methyl group. X is a single bond or a methylene group. R 1 to R 11 are each independently a hydrogen atom, a halogen atom, a nitro group or a cyano group, or may be substituted by a halogen atom, nitro Alkyl group or cyano substituted alkyl group having 1 to 20 carbons, alkoxy group having 1 to 20 carbons, aryl group having 6 to 20 carbons, aryloxy group having 6 to 20 carbons, 2 to 20 carbons Or a heteroaryloxy group having 2 to 20 carbons. Ar T is a phenyl substituted with di(aryl having 6 to 20 carbons) amino group. m is an integer of 0 to 2.) 2. Like the polymer of 1, wherein X is a single bond. 3. The polymer of 1 or 2, wherein R 1 to R 11 are hydrogen atoms. 4. The polymer according to any one of 1 to 3, wherein the aforementioned Ar T is p-(diphenylamino)phenyl, p-(1-naphthylphenylamino)phenyl, p-[di (1-naphthyl)amino]phenyl, p-(1-naphthyl-2-naphthylamino)phenyl, p-[bis(2-naphthyl)amino]phenyl. 5. The polymer according to any one of 1 to 4, wherein m is 0 or 1. 6. A charge-transporting paint containing (A) a charge-transporting substance containing a polymer such as any one of 1 to 5, and (B) an organic solvent. 7. The charge-transporting paint according to 6, which further contains (C) a dopant. 8. The charge-transporting paint according to 7, wherein the organic solvent contains a low-polarity organic solvent. 9. A charge-transporting film obtained from the charge-transporting paint of any one of 6-8. 10. An organic electroluminescence element, which is provided with a charge-transporting thin film such as 9. 11. The organic electroluminescence device according to 10, wherein the charge transporting thin film is a hole injection layer or a hole transport layer. 12. A monomer represented by the following formula (1').
Figure 02_image003
(In the formula, R A , X, R 1 to R 11 , Ar T and m are the same as described above.) [Effects of the invention]

本發明之聚合物因其主鏈不含共軛構造，故具備高透明性，因其側鏈具有咔唑部位，故具備高折射率，因其側鏈的末端具有三芳基胺基骨架同時具有柔軟的主鏈，故具備高溶解性，更且因包含具有同時含有咔唑部位與三芳基胺部位的電荷輸送性優異之側鏈的重複單位，故具備優異的電荷輸送性。The polymer of the present invention has high transparency because its main chain does not contain a conjugated structure, and because its side chain has a carbazole site, it has a high refractive index, and because the end of the side chain has a triarylamine group skeleton and has The soft main chain has high solubility, and it also contains a repeating unit having a side chain with excellent charge transportability containing both a carbazole site and a triarylamine site, so it has excellent charge transportability.

藉由使用包含如此之聚合物的本發明之電荷輸送性塗漆，可製作高透明性及高折射率的薄膜，又，即使在200℃以下之低溫進行燒成之情況，仍可製作電荷輸送性優異之薄膜。由本發明之電荷輸送性塗漆所得到的電荷輸送性薄膜，可使用作為以有機EL元件為首的電子元件用薄膜，藉由用作為有機EL元件的電洞注入層或電洞輸送層、尤其電洞注入層，可得到特性優異的有機EL元件。 [實施發明之最佳形態]By using the charge-transporting paint of the present invention containing such a polymer, a film with high transparency and high refractive index can be produced, and even if it is fired at a low temperature below 200°C, it can still be produced Excellent film. The charge-transporting film obtained by the charge-transporting paint of the present invention can be used as a thin film for electronic devices including organic EL devices, by being used as a hole injection layer or a hole transporting layer of an organic EL device, especially an electric The hole injection layer can provide an organic EL device with excellent characteristics. [Best form to implement invention]

[聚合物] 本發明之聚合物係含有下述式(1)所表示之重複單位者。

Figure 02_image005
[Polymer] The polymer of the present invention contains a repeating unit represented by the following formula (1).
Figure 02_image005

式(1)中，RA 為氫原子或甲基，但以氫原子為佳。In formula (1), R A is a hydrogen atom or a methyl group, but a hydrogen atom is preferred.

式(1)中，X為單鍵或亞甲基，但以單鍵為佳。In formula (1), X is a single bond or a methylene group, but a single bond is preferred.

式(1)中，R1 ～R11 各自獨立，為氫原子、鹵素原子、硝基或者氰基、或可被鹵素原子、硝基或者氰基取代的碳數1～20的烷基、碳數1～20的烷氧基、碳數6～20的芳基、碳數6～20的芳基氧基、碳數2～20的雜芳基或者碳數2～20的雜芳基氧基。In formula (1), R 1 to R 11 are each independent, and are a hydrogen atom, a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbons which may be substituted by a halogen atom, a nitro group or a cyano group, and carbon Alkoxy with 1-20, aryl with 6-20, aryloxy with 6-20, heteroaryl with 2-20, or heteroaryloxy with 2-20 .

前述鹵素原子方面，可舉例如氟原子、氯原子、溴原子、碘原子等，但以氟原子為佳。As for the aforementioned halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, but a fluorine atom is preferred.

前述碳數1～20的烷基，可為直鏈狀、分枝狀、環狀之任一皆可，其具體例方面，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、s-丁基、t-丁基、n-戊基、n-己基、n-庚基、n-辛基、n-壬基、n-癸基、n-十一基、n-十二基、n-十三基、n-十四基、n-十五基、n-十六基、n-十七基、n-十八基、n-十九基、n-二十基等之直鏈狀或分枝狀烷基；環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、雙環丁基、雙環戊基、雙環己基、雙環庚基、雙環辛基、雙環壬基、雙環癸基等之碳數3～20的環狀烷基等。The aforementioned C 1-20 alkyl group may be linear, branched, or cyclic. Specific examples thereof include methyl, ethyl, n-propyl, and isopropyl. , N-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n -Undecyl, n-dodecyl, n-thirteen, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-seventeen, n-octadecyl, n-dec Nonayl, n-eicosyl and other linear or branched alkyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl , Bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl and other cyclic alkyl groups with 3 to 20 carbon atoms.

前述碳數1～20的烷氧基，可為直鏈狀、分枝狀、環狀之任一皆可，其具體例方面，可舉例如甲氧基、乙氧基、n-丙氧基、異丙氧基、n-丁氧基、異丁氧基、s-丁氧基、t-丁氧基、n-戊基氧基、n-己基氧基、n-庚基氧基、n-辛基氧基、n-壬基氧基、n-癸基氧基等之碳數1～20之直鏈狀或分枝狀烷氧基；環丙基氧基、環丁基氧基、環戊基氧基、環己基氧基、環庚基氧基、環辛基氧基、環壬基氧基、環癸基氧基、雙環丁基氧基、雙環戊基氧基、雙環己基氧基、雙環庚基氧基、雙環辛基氧基、雙環壬基氧基、雙環癸基氧基等之碳數3～20的環狀烷氧基。The aforementioned C 1-20 alkoxy group may be linear, branched, or cyclic. Specific examples include methoxy, ethoxy, and n-propoxy. , Isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n -Octyloxy, n-nonyloxy, n-decyloxy and other linear or branched alkoxy groups with 1 to 20 carbon atoms; cyclopropyloxy, cyclobutyloxy, Cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, cyclodecyloxy, dicyclobutyloxy, dicyclopentyloxy, dicyclohexyloxy Cyclic alkoxy groups with 3 to 20 carbon atoms such as bicycloheptyloxy, bicyclooctyloxy, bicyclononyloxy, and bicyclodecyloxy.

前述碳數6～20的芳基方面，可舉例如苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等。Examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, and 2-phenanthrene. Base, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, etc.

前述碳數6～20的芳基氧基的具體例方面，可舉例如苯基氧基、1-萘基氧基、2-萘基氧基、1-蒽基氧基、2-蒽基氧基、9-蒽基氧基、1-菲基氧基、2-菲基氧基、3-菲基氧基、4-菲基氧基、9-菲基氧基等。Specific examples of the aryloxy group having 6 to 20 carbon atoms include, for example, phenyloxy, 1-naphthyloxy, 2-naphthyloxy, 1-anthryloxy, and 2-anthryloxy. Group, 9-anthryloxy, 1-phenanthryloxy, 2-phenanthryloxy, 3-phenanthryloxy, 4-phenanthryloxy, 9-phenanthryloxy, etc.

前述碳數2～20的雜芳基的具體例方面，可舉例如2-噻吩基、3-噻吩基、2-呋喃基、3-呋喃基、2-噁唑基、4-噁唑基、5-噁唑基、3-異噁唑基、4-異噁唑基、5-異噁唑基、2-噻唑基、4-噻唑基、5-噻唑基、3-異噻唑基、4-異噻唑基、5-異噻唑基、2-咪唑基、4-咪唑基、2-吡啶基、3-吡啶基、4-吡啶基等。Specific examples of the aforementioned heteroaryl groups having 2 to 20 carbon atoms include, for example, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4- Isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl and the like.

前述碳數2～20的雜芳基氧基的具體例方面，可舉例如2-噻吩基氧基、3-噻吩基氧基、2-呋喃基氧基、3-呋喃基氧基、2-噁唑基氧基、4-噁唑基氧基、5-噁唑基氧基、3-異噁唑基氧基、4-異噁唑基氧基、5-異噁唑基氧基、2-噻唑基氧基、4-噻唑基氧基、5-噻唑基氧基、3-異噻唑基氧基、4-異噻唑基氧基、5-異噻唑基氧基、2-咪唑基氧基、4-咪唑基氧基、2-吡啶基氧基、3-吡啶基氧基、4-吡啶基氧基等。Specific examples of the aforementioned heteroaryloxy group having 2 to 20 carbon atoms include, for example, 2-thienyloxy, 3-thienyloxy, 2-furyloxy, 3-furyloxy, 2- Oxazolyloxy, 4-oxazolyloxy, 5-oxazolyloxy, 3-isoxazolyloxy, 4-isoxazolyloxy, 5-isoxazolyloxy, 2 -Thiazolyloxy, 4-thiazolyloxy, 5-thiazolyloxy, 3-isothiazolyloxy, 4-isothiazolyloxy, 5-isothiazolyloxy, 2-imidazolyloxy , 4-imidazolyloxy, 2-pyridyloxy, 3-pyridyloxy, 4-pyridyloxy and the like.

此等中，R1 ～R11 方面，以氫原子、鹵素原子、碳數1～20的烷基為佳、氫原子、鹵素原子更佳、氫原子為最佳。Among these, among R 1 to R 11 , a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms are preferred, a hydrogen atom and a halogen atom are more preferred, and a hydrogen atom is most preferred.

式(1)中，ArT 為經二(碳數6～20的芳基)胺基取代的苯基，該二芳基胺基之碳數6～20的芳基的具體例方面，可舉例如與前述相同者。此等2個碳數6～20的芳基以相同為佳。二(碳數6～20的芳基)胺基方面，可舉例如二苯基胺基、1-萘基苯基胺基、二(1-萘基)胺基、1-萘基-2-萘基胺基、二(2-萘基)胺基等。又，二(碳數6～20的芳基)胺基以鍵結於苯基的4位或3位為佳、以鍵結於4位最佳。In the formula (1), Ar T is a phenyl group substituted with a di(aryl group having 6 to 20 carbons) amino group. Specific examples of the aryl group having 6 to 20 carbons of the diaryl amino group include Same as above. The two aryl groups having 6 to 20 carbons are preferably the same. As for the di(aryl group having 6 to 20 carbons) amino group, for example, diphenylamino group, 1-naphthylphenylamino group, di(1-naphthyl)amino group, 1-naphthyl-2- Naphthylamino, bis(2-naphthyl)amino, etc. In addition, the bis(aryl group having 6 to 20 carbons) amino group is preferably bonded to the 4-position or 3-position of the phenyl group, and is most preferably bonded to the 4-position.

ArT 方面，以p-(二苯基胺基)苯基、p-(1-萘基苯基胺基)苯基、p-[二(1-萘基)胺基]苯基、p-(1-萘基-2-萘基胺基)苯基、p-[二(2-萘基)胺基]苯基為佳、p-(二苯基胺基)苯基更佳。Ar T , p-(diphenylamino)phenyl, p-(1-naphthylphenylamino)phenyl, p-[bis(1-naphthyl)amino]phenyl, p- (1-naphthyl-2-naphthylamino)phenyl, p-[bis(2-naphthyl)amino]phenyl is preferred, and p-(diphenylamino)phenyl is more preferred.

式(1)中，m為0～2的整數，但以0或1更佳。In formula (1), m is an integer of 0-2, but 0 or 1 is more preferable.

本發明之聚合物可為僅含有1種式(1)所表示之重複單位者、亦可為含有2種以上式(1)所表示之重複單位者。又，在不損及本發明之效果範圍，可含有式(1)所表示之重複單位以外的重複單位。又，含有複數重複單位時，本發明之聚合物為隨機共聚物、交互共聚物、嵌段共聚物之任一皆可。The polymer of the present invention may contain only one type of repeating unit represented by formula (1), or may contain two or more types of repeating unit represented by formula (1). In addition, within a range that does not impair the effect of the present invention, repeating units other than the repeating unit represented by formula (1) may be included. In addition, when a plurality of repeating units are contained, the polymer of the present invention may be any of random copolymers, interactive copolymers, and block copolymers.

本發明中，式(1)所表示之重複單位的含量，在聚合物所含有的全重複單位中，以50莫耳%以上為佳、80莫耳%以上更佳、90莫耳%以上又更佳、95莫耳%以上再佳、100莫耳%最佳。In the present invention, the content of the repeating unit represented by the formula (1) is preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol% or more of the total repeating units contained in the polymer. More preferably, more than 95 mol% is best, and 100 mol% is the best.

本發明之聚合物的重量平均分子量(Mw)，通常為1,000～200,000，但由使聚合物的溶解性提升，再現性佳地得到均勻性優異的塗漆觀點，較佳為150,000以下、更佳為100,000以下。又，本發明中，Mw為膠體滲透層析法(GPC)之聚苯乙烯換算測定值。Mw及數平均分子量(Mn)，例如可使用(股)島津製作所製(管柱:Shodex GPC KF-805L+KF-804L、管柱溫度；40℃、偵測器:UV偵測器(254nm)、溶離液:四氫呋喃、管柱流速:1.0mL/min)之裝置進行測定。The weight-average molecular weight (Mw) of the polymer of the present invention is usually 1,000 to 200,000, but from the viewpoint of improving the solubility of the polymer and achieving good reproducibility, the uniformity of the painting is excellent, preferably 150,000 or less, more preferably Below 100,000. In addition, in the present invention, Mw is a polystyrene conversion value measured by colloidal permeation chromatography (GPC). Mw and number average molecular weight (Mn), for example, Shimadzu Corporation (Stock) can be used (column: Shodex GPC KF-805L+KF-804L, column temperature; 40℃, detector: UV detector (254nm) , Eluent: tetrahydrofuran, column flow rate: 1.0mL/min) device for determination.

[聚合物之製造方法] 式(1)所表示之聚合物可藉由將1種或2種以上的下述式(1’)所表示之單體聚合來製造。

Figure 02_image007
(式中，RA 、X、R1 ～R11 、m及ArT 同前述。)[Method for producing polymer] The polymer represented by the formula (1) can be produced by polymerizing one or more monomers represented by the following formula (1').
Figure 02_image007
(In the formula, R A , X, R 1 to R 11 , m and Ar T are the same as described above.)

聚合反應，不特別限制，可採用自由基聚合、陰離子聚合、陽離子聚合等。此等中，尤以自由基聚合為佳，具體上，於溶劑中使前述單體在聚合起始劑存在下進行加熱、使其聚合即可。The polymerization reaction is not particularly limited, and radical polymerization, anionic polymerization, cationic polymerization, etc. can be used. Among these, radical polymerization is particularly preferred. Specifically, the aforementioned monomers are heated in the presence of a polymerization initiator in a solvent to polymerize them.

前述聚合起始劑方面，可由以往已知者中適宜選擇使用。例如過氧化苯甲醯、異丙苯氫過氧化物(Cumene hydroperoxide)、t-丁基氫過氧化物等之過氧化物；過硫酸鈉、過硫酸鉀、過硫酸銨等之過硫酸鹽；偶氮二異丁腈(AIBN)、偶氮雙甲基丁腈、偶氮雙異戊腈等之偶氮系化合物等。此等可1種單獨或2種以上組合使用。The aforementioned polymerization initiator can be suitably selected and used from those known in the past. For example, benzyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide and other peroxides; sodium persulfate, potassium persulfate, ammonium persulfate and other persulfates; Azo compounds such as azobisisobutyronitrile (AIBN), azobismethylbutyronitrile, azobisisovaleronitrile, etc. These can be used alone or in combination of two or more.

聚合起始劑的使用量，相對於前述單體1mol，以0.01～0.05mol左右為佳。反應溫度可在0℃～使用之溶劑的沸點為止適宜設定即可，但以20～100℃左右為佳。反應時間以0.1～30小時左右為佳。The amount of the polymerization initiator used is preferably about 0.01 to 0.05 mol relative to 1 mol of the aforementioned monomer. The reaction temperature can be appropriately set from 0°C to the boiling point of the solvent used, but is preferably about 20 to 100°C. The reaction time is preferably about 0.1 to 30 hours.

聚合反應使用的溶劑從在該種反應一般使用的各種溶劑中適宜選擇即可。具體上，可舉例如水；甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、異丁醇、t-丁醇、1-戊醇、2-戊醇、3-戊醇、異戊醇、t-戊醇、1-己醇、1-庚醇、2-庚醇、3-庚醇、2-辛醇、2-乙基-1-己醇、苄基醇、環己醇等之醇類；二乙基醚、二異丙基醚、二丁基醚、環戊基甲基醚、四氫呋喃、1,4-二噁烷等之醚類；氯仿、二氯甲烷、二氯乙烷、四氯化碳等之鹵素化烴類；甲基溶纖劑、乙基溶纖劑、異丙基溶纖劑、丁基溶纖劑、二乙二醇單丁基醚等之醚醇類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等之酮類；乙酸乙基酯、乙酸丁基酯、丙酸乙基酯、溶纖劑乙酸酯等之酯類；n-戊烷、n-己烷、n-庚烷、n-辛烷、n-壬烷、n-癸烷、環戊烷、甲基環戊烷、環己烷、甲基環己烷、苯、甲苯、二甲苯、乙基苯、苯甲醚等之脂肪族或芳香族烴類；二甲縮醛(methylal)、二乙縮醛等之縮醛類；甲酸、乙酸、丙酸等之脂肪酸類；硝基丙烷、硝基苯、二甲基胺、單乙醇胺、吡啶、N-甲基-2-吡咯烷酮、N,N-二甲基甲醯胺、二甲基亞碸、乙腈等。此等可1種單獨或2種以上混合使用。The solvent used in the polymerization reaction may be appropriately selected from various solvents generally used in this type of reaction. Specifically, for example, water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, isopentanol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl Alcohols such as base alcohol and cyclohexanol; Diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane and other ethers; Chloroform, Halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride, etc.; methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl Ether and other ether alcohols; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; ethyl acetate, butyl acetate, ethyl propionate, cellosolve B Esters such as acid esters; n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclopentane, cyclohexane Aliphatic or aromatic hydrocarbons such as, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, anisole, etc.; acetals such as methylal and diethyl acetal; formic acid , Acetic acid, propionic acid and other fatty acids; nitropropane, nitrobenzene, dimethylamine, monoethanolamine, pyridine, N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethylamine Chia, acetonitrile, etc. These can be used alone or in combination of two or more.

又，本發明之聚合物含有式(1)所表示之重複單位以外的重複單位時，其合成方法方面，在聚合之際使式(1’)所表示之單體與賦予其他重複單位的單體共存進行聚合即可。In addition, when the polymer of the present invention contains a repeating unit other than the repeating unit represented by formula (1), in terms of its synthesis method, the monomer represented by formula (1') is combined with a monomer giving other repeating unit during polymerization. Coexistence and polymerization can be carried out.

式(1’)所表示之單體可藉由組合各種耦合反應來合成。例如如下述路徑表示般，可藉由使化合物(1A)與化合物(1B)進行耦合反應，合成式(1C)所表示之化合物(第1步驟)後，將其與格里那試劑(1D)反應(第2步驟)來合成。又，下述路徑中，表示R1 ～R11 為氫原子，m為1時之製造方法，但不限於此。

Figure 02_image009
(式中，ArT 及X同前述。XA 及XB 各自獨立，為鹵素原子或擬鹵素基。XC 為耦合反應所使用的任意之基。)The monomer represented by formula (1') can be synthesized by combining various coupling reactions. For example, as shown in the following route, the compound (1A) and the compound (1B) can be coupled to react to synthesize the compound represented by the formula (1C) (the first step), and then combine it with Gleaner’s reagent (1D) Reaction (2nd step) to synthesize. In addition, in the following path, R 1 to R 11 are hydrogen atoms, and m is a production method when m is 1, but it is not limited to this.
Figure 02_image009
(In the formula, Ar T and X are the same as described above. X A and X B are each independent and are a halogen atom or a pseudo-halogen group. X C is any group used in the coupling reaction.)

XA 及XB 所表示之鹵素原子方面，可舉例如與式(1)之R1 ～R11 的說明中，例示者相同者，但以溴原子或碘原子為佳。The halogen atoms represented by X A and X B include, for example, the same as those exemplified in the description of R 1 to R 11 of formula (1), but a bromine atom or an iodine atom is preferred.

XA 及XB 所表示之擬鹵素基方面，可舉例如甲磺醯基氧基、三氟甲磺醯基氧基、九氟丁烷磺醯基氧基等之氟烷基磺醯基氧基；苯磺醯基氧基、甲苯磺醯基氧基等之芳香族磺醯基氧基等。The pseudo-halogen groups represented by X A and X B include, for example, fluoroalkylsulfonyloxy groups such as methanesulfonyloxy, trifluoromethanesulfonyloxy, nonafluorobutanesulfonyloxy, etc. Group; Aromatic sulfonyloxy such as benzenesulfonyloxy, toluenesulfonyloxy and the like.

第1步驟中使用之溶劑方面，為不對反應有負面影響者則不特別限定，可舉例如脂肪族烴(戊烷、n-己烷、n-辛烷、n-癸烷、萘烷等)、鹵素化脂肪族烴(氯仿、二氯甲烷、二氯乙烷、四氯化碳等)、芳香族烴(苯、硝基苯、甲苯、o-二甲苯、m-二甲苯、p-二甲苯、均三甲苯等)、醚(二乙基醚、二異丙基醚、t-丁基甲基醚、四氫呋喃(THF)、二噁烷、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷等)、醯胺(N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺等)、內醯胺及內酯(N-甲基吡咯烷酮、γ-丁內酯等)、尿素衍生物(N,N-二甲基咪唑啉酮、四甲基脲等)、亞碸(二甲基亞碸、環丁碸等)、腈(乙腈、丙腈、丁腈等)等。此等中，由有效率得到目的物觀點，較佳溶劑為脂肪族烴(戊烷、n-己烷、n-辛烷、n-癸烷、萘烷等)、芳香族烴(苯、硝基苯、甲苯、o-二甲苯、m-二甲苯、p-二甲苯、均三甲苯等)、醚(二乙基醚、二異丙基醚、t-丁基甲基醚、THF、二噁烷、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷等)，更佳為芳香族烴(苯、硝基苯、甲苯、o-二甲苯、m-二甲苯、p-二甲苯、均三甲苯等)、醚(二乙基醚、二異丙基醚、t-丁基甲基醚、THF、二噁烷、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷等)。The solvent used in the first step is not particularly limited as long as it does not adversely affect the reaction. Examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.) , Halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-di Toluene, mesitylene, etc.), ether (diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane, 1, 2 -Diethoxyethane, etc.), amides (N,N-dimethylformamide (DMF), N,N-dimethylacetamide, etc.), lactones and lactones (N-methyl Pyrrolidone, γ-butyrolactone, etc.), urea derivatives (N,N-dimethylimidazolinone, tetramethylurea, etc.), sulfinium (dimethyl sulfoxide, cyclobutane, etc.), nitrile ( Acetonitrile, propionitrile, butyronitrile, etc.). Among these, from the viewpoint of efficiently obtaining the target, the preferred solvents are aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), aromatic hydrocarbons (benzene, nitrobenzene, etc.) Benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), ether (diethyl ether, diisopropyl ether, t-butyl methyl ether, THF, dioxane) , 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), more preferably aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), ether (diethyl ether, diisopropyl ether, t-butyl methyl ether, THF, dioxane, 1,2-dimethoxyethane, 1, 2 -Diethoxyethane etc.).

第1步驟中使用之觸媒方面，可舉例如[1,1’-雙(二苯基膦基)二茂鐵]鈀(II)二氯化物(PdCl2 (dppf))、肆(三苯基膦)鈀(Pd(PPh3 )4 )、雙(三苯基膦)二氯鈀(Pd(PPh3 )2 Cl2 )、雙(亞苄基丙酮)鈀(Pd(dba)2 )、參(亞苄基丙酮)二鈀(Pd2 (dba)3 )、雙(三t-丁基膦)鈀(Pd(P-t-Bu3 )2 )、乙酸鈀(II)(Pd(OAc)2 )等之鈀觸媒等。此等之觸媒可與習知適當的配位基一起使用。The catalyst used in the first step includes, for example, [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (PdCl 2 (dppf)), tetraphenyl Phosphine) palladium (Pd(PPh 3 ) 4 ), bis(triphenylphosphine) palladium dichloride (Pd(PPh 3 ) 2 Cl 2 ), bis(benzylideneacetone) palladium (Pd(dba) 2 ), Ginseng (benzylidene acetone) two palladium (Pd 2 (dba) 3 ), bis(trit-butylphosphine) palladium (Pd(Pt-Bu 3 ) 2 ), palladium(II) acetate (Pd(OAc) 2 ) And other palladium catalysts. These catalysts can be used together with conventional appropriate ligands.

觸媒的使用量相對化合物(1A)，以莫耳比計可為0.001～0.5，但以0.005～0.1左右為宜。又，使用配位基時，其使用量相對使用的金屬錯合物，可為1～10當量，但以1～4當量為宜。The amount of the catalyst used relative to compound (1A) can be 0.001 to 0.5 in molar ratio, but is preferably about 0.005 to 0.1. In addition, when a ligand is used, the amount used may be 1-10 equivalents relative to the metal complex used, but it is preferably 1 to 4 equivalents.

又，耦合反應中，可使用鹼。前述鹼方面，可舉例如氫氧化鋰、氫氧化鈉、氫氧化鉀等之氫氧化鹼金屬；t-丁氧基鋰、t-丁氧基鈉、t-丁氧基鉀等之烷氧基鹼金屬；碳酸鈉、碳酸鉀等之碳酸鹼金屬；碳酸氫鈉、碳酸氫鉀等之碳酸氫鹼金屬；碳酸鈣等之碳酸鹼土類金屬；n-丁基鋰、s-丁基鋰、t-丁基鋰等之有機鋰；三乙基胺、二異丙基乙基胺、四甲基伸乙二胺、三伸乙二胺、吡啶等之胺類等，但為該種反應可使用者則不特別限定。尤其，由操作容易點來看，以碳酸鈉、碳酸鉀為宜。前述鹼的使用量相對化合物(1A)，以莫耳比計通常為1～20左右、較佳為4～8。In addition, a base can be used in the coupling reaction. In terms of the aforementioned bases, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.; alkoxy groups such as lithium t-butoxide, sodium t-butoxide, potassium t-butoxide, etc. Alkali metals; alkali metals such as sodium carbonate and potassium carbonate; alkali metals such as sodium bicarbonate and potassium bicarbonate; alkaline earth metals such as calcium carbonate; n-butyllithium, s-butyllithium, t -Organic lithium such as butyl lithium; amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, pyridine, etc., but can be used for this kind of reaction It is not particularly limited. In particular, in view of ease of operation, sodium carbonate and potassium carbonate are suitable. The use amount of the aforementioned base is usually about 1-20, preferably 4-8 in terms of molar ratio with respect to compound (1A).

第1步驟中，化合物(1A)與化合物(1B)之添加比，相對於化合物(1A)，化合物(1B)莫耳比計以1～2為佳、1～1.2更佳。In the first step, the addition ratio of compound (1A) to compound (1B) is preferably 1 to 2, and more preferably 1 to 1.2 in molar ratio of compound (1B) relative to compound (1A).

第1步驟中，反應溫度係一邊考量使用之原料化合物或觸媒的種類或量，一邊在溶劑的熔點到沸點為止之範圍適宜設定，通常為0～200℃左右、較佳為20～80℃。又，反應時間因使用的原料化合物或反應溫度等而異，一般無法指定，但通常為1～24小時左右。In the first step, the reaction temperature is appropriately set in the range from the melting point of the solvent to the boiling point while considering the type or amount of the raw material compound or catalyst used, and is usually about 0 to 200°C, preferably 20 to 80°C . In addition, the reaction time varies depending on the raw material compound used, the reaction temperature, etc., and generally cannot be specified, but it is usually about 1 to 24 hours.

第2步驟中使用之溶劑及觸媒方面，可舉例如與作為第1步驟使用的溶劑及觸媒例示者相同者。The solvent and catalyst used in the second step may be, for example, the same as those exemplified as the solvent and catalyst used in the first step.

第2步驟中，化合物(1C)與化合物(1D)之添加比，相對於化合物(1C)，化合物(1D)莫耳比計以1～5為佳、1～3更佳。In the second step, the addition ratio of compound (1C) to compound (1D) is preferably 1 to 5, and more preferably 1 to 3 in terms of molar ratio of compound (1D) relative to compound (1C).

第2步驟中，反應溫度係一邊考量使用的原料化合物或觸媒的種類或量，一邊在溶劑的熔點到沸點為止之範圍適宜設定，但通常為0～200℃左右、較佳為20～80℃。又，反應時間因為因使用的原料化合物或反應溫度等而異，一般無法指定，但通常為1～24小時左右。In the second step, the reaction temperature is appropriately set in the range from the melting point of the solvent to the boiling point while considering the type or amount of the raw material compound or catalyst used, but is usually about 0 to 200°C, preferably 20 to 80 ℃. In addition, the reaction time varies depending on the raw material compound used, the reaction temperature, etc., and generally cannot be specified, but it is usually about 1 to 24 hours.

反應完畢後依據普通方法進行後處理，可得到目的之單體。After the reaction is completed, post-treatment is performed according to common methods to obtain the desired monomer.

[電荷輸送性塗漆] 本發明之電荷輸送性塗漆為含有(A)含有式(1)所表示之聚合物的電荷輸送性物質、及(B)有機溶劑者。又，本發明中，電荷輸送性與導電性同義，且與電洞輸送性同義。[Charge transport paint] The charge-transporting paint of the present invention contains (A) a charge-transporting substance containing the polymer represented by formula (1), and (B) an organic solvent. In addition, in the present invention, charge transportability is synonymous with conductivity, and also synonymous with hole transportability.

(A)成分的式(1)所表示之聚合物單獨或與摻雜劑組合時，具有電荷輸送性物質之機能。又，電荷輸送性物質以皆於前述溶劑完全溶解、或均勻分散狀態為佳、以完全溶解更佳。(A) When the polymer represented by formula (1) of the component is used alone or in combination with a dopant, it has the function of a charge transporting substance. In addition, the charge-transporting substance is preferably completely dissolved in the aforementioned solvent or uniformly dispersed, and more preferably completely dissolved.

[(B)有機溶劑] (B)成分的有機溶劑方面，可使用能使前述聚合物良好溶解之高溶解性溶劑。為了將前述聚合物溶解且得到非晶質的塗膜，以使用低極性溶劑為佳。又，因應必要可併用低極性溶劑與高極性溶劑。又，本發明中，定義低極性溶劑為在頻率100kHz的相對介電常數未達7者，高極性溶劑為在頻率100kHz的相對介電常數為7以上者。[(B) Organic solvent] As for the organic solvent of the component (B), a highly soluble solvent that can dissolve the aforementioned polymer well can be used. In order to dissolve the aforementioned polymer and obtain an amorphous coating film, it is preferable to use a low-polarity solvent. In addition, a low-polarity solvent and a high-polarity solvent can be used together as necessary. In the present invention, a low-polarity solvent is defined as having a relative permittivity of less than 7 at a frequency of 100 kHz, and a high-polarity solvent is defined as having a relative permittivity of 7 or more at a frequency of 100 kHz.

低極性溶劑方面，可舉例如氯仿、氯苯等之氯系溶劑；甲苯、二甲苯、四氫化萘、環己基苯、癸基苯等之芳香族烴系溶劑、1-辛醇、1-壬醇、1-癸醇等之脂肪族醇系溶劑；四氫呋喃、二噁烷、苯甲醚、4-甲氧基甲苯、3-苯氧基甲苯、二苄基醚、二乙二醇二甲基醚、二乙二醇丁基甲基醚、三乙二醇二甲基醚、三乙二醇丁基甲基醚等之醚系溶劑；安息香酸甲基酯、安息香酸乙基酯、安息香酸丁基酯、安息香酸異戊基酯、鄰苯二甲酸雙(2-乙基己基)酯、馬來酸二丁基酯、草酸二丁基酯、乙酸己基酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯等之酯系溶劑等。Low-polarity solvents include, for example, chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene, 1-octanol, 1-nonane Aliphatic alcohol solvents such as alcohol and 1-decanol; tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl Ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether and other ether solvents; methyl benzoate, ethyl benzoate, butyl benzoate, Isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, diethylene glycol monoethyl ether acetate , Ester solvents such as diethylene glycol monobutyl ether acetate, etc.

又，高極性溶劑方面，可舉例如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二甲基異丁基醯胺、N-甲基吡咯烷酮、1,3-二甲基-2-咪唑啉酮等之醯胺系溶劑；乙基甲基酮、異佛爾酮、環己酮等之酮系溶劑；乙腈、3-甲氧基丙腈等之氰基系溶劑；乙二醇、二乙二醇、三乙二醇、二丙二醇、1,3-丁二醇、2,3-丁二醇等之多元醇系溶劑；二乙二醇單甲基醚、二乙二醇單苯基醚、三乙二醇單甲基醚、二丙二醇單甲基醚、苄基醇、2-苯氧基乙醇、2-苄基氧基乙醇、3-苯氧基苄基醇、四氫糠基醇等之脂肪族醇以外的1價醇系溶劑；二甲基亞碸等之亞碸系溶劑等。In addition, the highly polar solvents include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, and N-methylpyrrolidone , 1,3-Dimethyl-2-imidazolinone and other amide solvents; ethyl methyl ketone, isophorone, cyclohexanone and other ketone solvents; acetonitrile, 3-methoxypropionitrile Cyano-based solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 2,3-butanediol and other polyol solvents; diethylene glycol Monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3 -Monovalent alcohol-based solvents other than aliphatic alcohols such as phenoxybenzyl alcohol and tetrahydrofurfuryl alcohol; sulfenite-based solvents such as dimethyl sulfoxide, etc.

[(C)摻雜劑(電荷接受性摻雜劑)] 本發明之電荷輸送性塗漆以提升本發明之電荷輸送性塗漆所得到的薄膜的電荷輸送性等之目的，可含有摻雜劑。又，本發明中，摻雜劑中亦可包含藉由例如加熱般外部刺激而作為摻雜劑之機能提升或表現之物質，其具體例方面，可舉例如芳基磺酸酯化合物。[(C) Dopant (charge-accepting dopant)] The charge-transporting paint of the present invention may contain a dopant for the purpose of improving the charge transportability of the film obtained by the charge-transporting paint of the present invention. In addition, in the present invention, the dopant may also include a substance that improves or expresses the function of the dopant by an external stimulus such as heating. Specific examples thereof include arylsulfonate compounds.

前述摻雜劑方面，可使用以往已知的者，但由本發明之電荷輸送性塗漆所得到的薄膜的透明性的點，以下述式(2)所表示之離子化合物為佳。

Figure 02_image011
As for the aforementioned dopant, a conventionally known one can be used, but for the transparency of the film obtained by the charge-transporting paint of the present invention, an ionic compound represented by the following formula (2) is preferred.
Figure 02_image011

式(2)中，E為長週期型週期表的第13族元素，Ar1 ～Ar4 各自獨立，為碳數6～20的芳基或碳數2～20的雜芳基，且可被氟原子、氯原子、溴原子等之鹵素原子、氰基、硝基、乙醯基等之碳數2～12的醯基、或三氟甲基等之碳數1～10的鹵素化烷基取代。In formula (2), E is a group 13 element of the long-period periodic table, and Ar 1 to Ar 4 are independent of each other, and are aryl groups with 6 to 20 carbons or heteroaryl groups with 2 to 20 carbons, and can be Halogen atom such as fluorine atom, chlorine atom, bromine atom, cyano group, nitro group, acetyl group such as C 2-12 acyl group, or trifluoromethyl group such as C 1-10 halogenated alkyl group replace.

前述第13族元素方面，以硼原子、鋁原子、鎵原子為佳、硼原子更佳。碳數6～20的芳基及碳數2～20的雜芳基方面，可舉例如與式(1)之R1 ～R11 的說明中例示者相同者。With regard to the aforementioned Group 13 elements, boron atoms, aluminum atoms, and gallium atoms are preferred, and boron atoms are more preferred. The aryl group having 6 to 20 carbon atoms and the heteroaryl group having 2 to 20 carbon atoms are, for example, the same as those exemplified in the description of R 1 to R 11 in formula (1).

式(2)中，M+ 為鎓離子。前述鎓離子方面，可舉例如錪離子、鋶離子、銨離子、鏻離子等，尤其，以下述式(3)所表示之錪離子為佳。

Figure 02_image013
In the formula (2), M + is an onium ion. Examples of the aforementioned onium ion include iodonium ion, sulfonium ion, ammonium ion, phosphonium ion, and the like. In particular, the iodonium ion represented by the following formula (3) is preferred.
Figure 02_image013

式(3)中，R101 及R102 各自獨立，為碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數6～20的芳基或碳數2～20的雜芳基，亦可被鹵素原子、氰基、硝基、碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數6～20的芳基或碳數2～20的雜芳基取代。In the formula (3), R 101 and R 102 are independent of each other and are alkyl groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, alkynyl groups having 2 to 12 carbons, and aryl groups having 6 to 20 carbons. Or a heteroaryl group having 2 to 20 carbons, which may also be substituted by halogen atoms, cyano groups, nitro groups, alkyl groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, alkynyl groups having 2 to 12 carbons, It is substituted with an aryl group having 6 to 20 carbons or a heteroaryl group having 2 to 20 carbons.

又，由本發明之電荷輸送性塗漆所得到的薄膜的透明性的點，芳基磺酸化合物、芳基磺酸酯化合物等之磺酸化合物亦宜作為摻雜劑。In addition, at the point of transparency of the film obtained by the charge-transporting paint of the present invention, sulfonic acid compounds such as arylsulfonic acid compounds and arylsulfonic acid ester compounds are also suitable as dopants.

前述芳基磺酸化合物方面，以下述式(4)或(5)所表示者為佳。

Figure 02_image015
The aforementioned arylsulfonic acid compound is preferably represented by the following formula (4) or (5).
Figure 02_image015

式(4)中，A1 為-O-或-S-，但以-O-為佳。A2 為萘環或蒽環，但以萘環為佳。A3 為2～4價全氟聯苯基。p1 為A1 與A3 之結合數，為符合2≦p1 ≦4之整數，但以A3 為2價全氟聯苯基且p1 為2為佳。p2 為鍵結於A2 之磺酸基數，且符合1≦p2 ≦4之整數，但以2為宜。In formula (4), A 1 is -O- or -S-, but -O- is preferred. A 2 is a naphthalene ring or an anthracene ring, but a naphthalene ring is preferred. A 3 is a 2- to 4-valent perfluorobiphenyl group. p 1 is the bonding number of A 1 and A 3 , and is an integer satisfying 2≦p 1 ≦4, but it is preferable that A 3 is a divalent perfluorobiphenyl group and p 1 is 2. p 2 is the number of sulfonic acid groups bonded to A 2 and conforms to an integer of 1≦p 2 ≦4, but 2 is preferable.

式(5)中，A4 ～A8 各自獨立，為氫原子、鹵素原子、氰基、碳數1～20的烷基、碳數1～20的鹵素化烷基或碳數2～20的鹵素化烯基，但A4 ～A8 中至少3個為鹵素原子。q為鍵結於萘環的磺酸基數，且符合1≦q≦4之整數，但以2～4為佳、2更佳。In formula (5), A 4 to A 8 are each independent, and are a hydrogen atom, a halogen atom, a cyano group, a C 1-20 alkyl group, a C 1-20 halogenated alkyl group, or a C 2-20 Halogenated alkenyl, but at least 3 of A 4 to A 8 are halogen atoms. q is the number of sulfonic acid groups bonded to the naphthalene ring and conforms to an integer of 1≦q≦4, but 2 to 4 are preferable, and 2 is more preferable.

A4 ～A8 所表示之碳數1～20的鹵素化烷基方面，可舉例如三氟甲基、2,2,2-三氟乙基、全氟乙基、3,3,3-三氟丙基、2,2,3,3,3-五氟丙基、全氟丙基、4,4,4-三氟丁基、3,3,4,4,4-五氟丁基、2,2,3,3,4,4,4-七氟丁基、全氟丁基等。A4 ～A8 所表示之碳數2～20的鹵素化烯基方面，可舉例如全氟乙烯基、1-全氟丙烯基、全氟烯丙基、全氟丁烯基等。Examples of the halogenated alkyl groups having 1 to 20 carbons represented by A 4 to A 8 include trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 3,3,3- Trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, perfluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl , 2,2,3,3,4,4,4-heptafluorobutyl, perfluorobutyl, etc. Examples of the halogenated alkenyl groups having 2 to 20 carbons represented by A 4 to A 8 include perfluorovinyl, 1-perfluoropropenyl, perfluoroallyl, and perfluorobutenyl.

A4 ～A8 所表示之鹵素原子及碳數1～20的烷基方面，可舉例如與式(1)之R1 ～R11 的說明中例示者相同者，但鹵素原子方面，以氟原子為佳。The halogen atoms represented by A 4 to A 8 and the alkyl group having 1 to 20 carbons include, for example, the same ones as those exemplified in the description of R 1 to R 11 of formula (1). However, the halogen atom is fluorine Atoms are better.

此等中，以A4 ～A8 為氫原子、鹵素原子、氰基、碳數1～10的烷基、碳數1～10的鹵素化烷基或碳數2～10的鹵素化烯基，且A4 ～A8 中至少3個為氟原子為佳，以氫原子、氟原子、氰基、碳數1～5的烷基、碳數1～5的氟化烷基或碳數2～5的氟化烯基，且A4 ～A8 中至少3個為氟原子較佳，以氫原子、氟原子、氰基、碳數1～5的全氟烷基或碳數1～5的全氟烯基，且A4 、A5 及A8 為氟原子更佳。Among these, A 4 to A 8 are hydrogen atoms, halogen atoms, cyano groups, alkyl groups having 1 to 10 carbons, halogenated alkyl groups having 1 to 10 carbons, or halogenated alkenyl groups having 2 to 10 carbons. , And at least three of A 4 to A 8 are preferably fluorine atoms, hydrogen atom, fluorine atom, cyano group, C1-C5 alkyl group, C1-C5 fluorinated alkyl group or C2-C2 ~5 fluorinated alkenyl groups, and at least 3 of A 4 to A 8 are preferably fluorine atoms, preferably hydrogen atoms, fluorine atoms, cyano groups, perfluoroalkyl groups with 1 to 5 carbons or 1 to 5 carbons It is more preferable that A 4 , A 5 and A 8 are fluorine atoms.

又，全氟烷基為烷基的氫原子全部被氟原子取代的基，全氟烯基為烯基的氫原子全部被氟原子取代的基。In addition, a perfluoroalkyl group is a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms, and a perfluoroalkenyl group is a group in which all hydrogen atoms of an alkenyl group are substituted with fluorine atoms.

適宜之芳基磺酸化合物的具體例方面，可舉例如以下所示者，但不限於此等。

Figure 02_image017
Specific examples of suitable arylsulfonic acid compounds include those shown below, but are not limited to these.
Figure 02_image017

前述芳基磺酸酯化合物方面，可舉例如國際公開第2017/217455號所揭示的芳基磺酸酯化合物、國際公開第2017/217457號所揭示的芳基磺酸酯化合物、特願2017-243631記載之芳基磺酸酯化合物等。The aforementioned aryl sulfonate compound includes, for example, the aryl sulfonate compound disclosed in International Publication No. 2017/217455, the aryl sulfonate compound disclosed in International Publication No. 2017/217457, and Japanese Patent Application No. 2017- The aryl sulfonate compound described in 243631.

具體上，前述芳基磺酸酯化合物方面，以下述式(6)～(8)所表示者為佳。

Figure 02_image019
Figure 02_image021
Specifically, the aforementioned arylsulfonate compound is preferably represented by the following formulas (6) to (8).
Figure 02_image019
Figure 02_image021

式(6)～(8)中，m為符合1≦m≦4的整數，但以2為佳。n為符合1≦n≦4的整數，但以2為佳。In formulas (6) to (8), m is an integer satisfying 1≦m≦4, but 2 is preferred. n is an integer satisfying 1≦n≦4, but 2 is preferred.

式(6)中，A11 為全氟聯苯基所衍生的m價基(即，從全氟聯苯基除去m個氟原子而得到的基)。A12 為  -O-或-S-，但以-O-為佳。A13 為萘或蒽所衍生的(n+1)價基(即，從萘或蒽除去n+1個氫原子而得到的基)，但以萘所衍生的基為佳。Rs1 ～Rs4 各自獨立，為氫原子、或直鏈狀或者分枝狀的碳數1～6的烷基，Rs5 為可經取代的碳數2～20的1價烴基。In the formula (6), A 11 is an m-valent group derived from a perfluorobiphenyl group (that is, a group obtained by removing m fluorine atoms from a perfluorobiphenyl group). A 12 is -O- or -S-, but -O- is preferred. A 13 is an (n+1) valent group derived from naphthalene or anthracene (that is, a group obtained by removing n+1 hydrogen atoms from naphthalene or anthracene), but a group derived from naphthalene is preferred. R s1 to R s4 are independent of each other and are a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbons, and R s5 is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbons.

Rs1 ～Rs4 所表示之直鏈狀或分枝狀的碳數1～6的烷基方面，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、t-丁基、n-己基等。此等中，以碳數1～3的烷基為佳。尤其，以Rs1 ～Rs4 中，Rs1 或Rs3 為碳數1～3之直鏈烷基且其餘為氫原子、或Rs1 為碳數1～3之直鏈烷基且Rs2 ～Rs4 為氫原子為佳。該場合，碳數1～3之直鏈烷基方面，以甲基為佳。 Regarding the linear or branched alkyl group having 1 to 6 carbon atoms represented by R s1 to R s4 , for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso Butyl, t-butyl, n-hexyl, etc. Among these, an alkyl group having 1 to 3 carbon atoms is preferred. In particular, in R s1 to R s4 , R s1 or R s3 is a linear alkyl group with 1 to 3 carbons and the rest are hydrogen atoms, or R s1 is a linear alkyl group with 1 to 3 carbons and R s2 to R s4 is preferably a hydrogen atom. In this case, the straight-chain alkyl group having 1 to 3 carbon atoms is preferably a methyl group.

Rs5 所表示之碳數2～20的1價烴基，可為直鏈狀、分枝狀、環狀之任一皆可，其具體例方面，可舉例如乙基、n-丙基、異丙基、n-丁基、異丁基、t-丁基等之烷基；苯基、萘基、菲基等之芳基等。此等中，Rs5 方面，以碳數2～4之直鏈烷基或苯基為佳。The monovalent hydrocarbon group with 2 to 20 carbon atoms represented by R s5 may be linear, branched, or cyclic. Specific examples include ethyl, n-propyl, iso Alkyl groups such as propyl, n-butyl, isobutyl and t-butyl; aryl groups such as phenyl, naphthyl, and phenanthryl. Among these, R s5 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group.

式(7)中，A14 為可經取代的含有1個以上之芳香環的碳數6～20的m價烴基，該烴基為從含有1個以上之芳香環的碳數6～20的烴化合物除去m個氫原子而得到的基。前述烴化合物方面，可舉例如苯、甲苯、二甲苯、乙基苯、聯苯、萘、蒽、菲等。此等中，A14 方面，以苯、聯苯等所衍生的基為佳。In the formula (7), A 14 is an m-valent hydrocarbon group with 6 to 20 carbons containing one or more aromatic rings which may be substituted, and the hydrocarbon group is a hydrocarbon group with 6 to 20 carbons containing one or more aromatic rings. A compound obtained by removing m hydrogen atoms. Examples of the aforementioned hydrocarbon compound include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, and phenanthrene. Among these, A 14 is preferably a group derived from benzene, biphenyl, etc.

又，前述烴基，其氫原子的一部分或全部可進而經取代基取代，如此之取代基方面，可舉例如氟原子、氯原子、溴原子、碘原子、硝基、氰基、羥基、胺基、矽烷醇基、硫醇基、羧基、磷酸基、1價烴基、有機氧基、有機胺基、有機矽烷基、有機硫基、醯基、磺基等。In addition, in the aforementioned hydrocarbon group, part or all of its hydrogen atoms may be further substituted with substituents. Examples of such substituents include fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, cyano group, hydroxyl group, and amino group. , Silanol group, thiol group, carboxyl group, phosphoric acid group, monovalent hydrocarbon group, organic oxygen group, organic amine group, organosilyl group, organothio group, sulfo group, etc.

式(7)中，A15 為-O-或-S-，但以-O-為佳。In formula (7), A 15 is -O- or -S-, but -O- is preferred.

式(7)中，A16 為碳數6～20的(n+1)價芳香族烴基，該芳香族烴基為從碳數6～20的芳香族烴化合物的芳香環上除去(n+1)個氫原子而得到的基。前述芳香族烴基化合物方面，可舉例如苯、甲苯、二甲苯、聯苯、萘、蒽、芘等。此等中，A16 方面，以萘或蒽所衍生的基為佳、萘所衍生的基更佳。In formula (7), A 16 is a (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbons, and the aromatic hydrocarbon group is removed from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbons (n+1 ) A hydrogen atom. Examples of the aforementioned aromatic hydrocarbon-based compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene. In these, A 16 aspect, anthracene or naphthalene group preferably derived, more preferably groups derived from naphthalene.

式(7)中，Rs6 及Rs7 各自獨立，為氫原子、或直鏈狀或者分枝狀的1價脂肪族烴基，Rs8 為直鏈狀或分枝狀的1價脂肪族烴基。但，Rs6 、Rs7 及Rs8 的碳數之合計為6以上。Rs6 、Rs7 及Rs8 的碳數合計的上限雖不特別限制，但以20以下為佳、10以下更佳。In formula (7), R s6 and R s7 are independent of each other and are a hydrogen atom, or a linear or branched monovalent aliphatic hydrocarbon group, and R s8 is a linear or branched monovalent aliphatic hydrocarbon group. However, the total carbon number of R s6 , R s7 and R s8 is 6 or more. Although the upper limit of the total carbon number of R s6 , R s7 and R s8 is not particularly limited, it is preferably 20 or less, and more preferably 10 or less.

Rs6 、Rs7 及Rs8 所表示之直鏈狀或分枝狀的1價脂肪族烴基的具體例方面，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、t-丁基、n-己基、n-辛基、2-乙基己基、癸基等之碳數1～20的烷基；乙烯基、1-丙烯基、2-丙烯基、異丙烯基、1-甲基-2-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、己烯基等之碳數2～20的烯基等。此等中，Rs6 以氫原子為佳、Rs7 及Rs8 各自獨立，以碳數1～6的烷基為佳。Specific examples of the linear or branched monovalent aliphatic hydrocarbon group represented by R s6 , R s7 and R s8 include, for example, methyl, ethyl, n-propyl, isopropyl, and n-butyl Alkyl group, isobutyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group and other C1-C20 alkyl groups; vinyl group, 1-propenyl group, 2-propenyl group Alkenyl groups with 2 to 20 carbon atoms such as 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and hexenyl. Among these, R s6 is preferably a hydrogen atom, R s7 and R s8 are each independent, and an alkyl group having 1 to 6 carbon atoms is preferred.

式(8)中，Rs9 ～Rs13 各自獨立，為氫原子、硝基、氰基、鹵素原子、碳數1～10的烷基、碳數1～10的鹵素化烷基或碳數2～10的鹵素化烯基。In the formula (8), R s9 to R s13 are each independently a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbons, a halogenated alkyl group having 1 to 10 carbons, or 2 ～10 halogenated alkenyl.

Rs9 ～Rs13 所表示之碳數1～10的烷基，可為直鏈狀、分枝狀、環狀之任一皆可，其具體例方面，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、s-丁基、t-丁基、n-戊基、環戊基、n-己基、環己基、n-庚基、n-辛基、n-壬基、n-癸基等。The alkyl group having 1 to 10 carbon atoms represented by R s9 to R s13 may be linear, branched, or cyclic. Specific examples include methyl, ethyl, n -Propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n- Octyl, n-nonyl, n-decyl, etc.

Rs9 ～Rs13 所表示之碳數1～10的鹵素化烷基為前述碳數1～10的烷基的氫原子的一部分或全部被鹵素原子取代的基，則不特別限制。其具體例方面，可舉例如三氟甲基、2,2,2-三氟乙基、1,1,2,2,2-五氟乙基、3,3,3-三氟丙基、2,2,3,3,3-五氟丙基、1,1,2,2,3,3,3-七氟丙基、4,4,4-三氟丁基、3,3,4,4,4-五氟丁基、2,2,3,3,4,4,4-七氟丁基、1,1,2,2,3,3,4,4,4-九氟丁基等。The halogenated alkyl group having 1 to 10 carbons represented by R s9 to R s13 is a group in which part or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 10 carbons are substituted with halogen atoms, and there is no particular limitation. Specific examples thereof include, for example, trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-Pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4 ,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl Base etc.

Rs9 ～Rs13 所表示之碳數2～10的鹵素化烯基方面，為碳數2～10的烯基的氫原子的一部分或全部被鹵素原子取代的基則不特別限制，其具體例方面，可舉例如全氟乙烯基、全氟-1-丙烯基、全氟-2-丙烯基、全氟-1-丁烯基、全氟-2-丁烯基、全氟-3-丁烯基等。 Regarding the halogenated alkenyl groups having 2 to 10 carbons represented by R s9 to R s13 , there are no particular restrictions on the groups in which part or all of the hydrogen atoms of the alkenyl group having 2 to 10 carbons are substituted by halogen atoms, and specific examples thereof Aspects, for example, perfluorovinyl, perfluoro-1-propenyl, perfluoro-2-propenyl, perfluoro-1-butenyl, perfluoro-2-butenyl, perfluoro-3-butenyl Alkenyl etc.

此等中，Rs9 方面，以硝基、氰基、碳數1～10的鹵素化烷基、碳數2～10的鹵素化烯基為佳、以硝基、氰基、碳數1～4的鹵素化烷基、碳數2～4的鹵素化烯基更佳、以硝基、氰基、三氟甲基、全氟丙烯基再佳。Rs10 ～Rs13 方面，以鹵素原子為佳、氟原子更佳。Among these, R s9 is preferably nitro, cyano, halogenated alkyl having 1 to 10 carbons, and halogenated alkenyl having 2 to 10 carbons, preferably nitro, cyano, and carbon 1 to The halogenated alkyl group of 4 and the halogenated alkenyl group having 2 to 4 carbon atoms are more preferable, and the nitro group, cyano group, trifluoromethyl group, and perfluoropropenyl group are more preferable. For R s10 to R s13 , a halogen atom is preferred, and a fluorine atom is more preferred.

式(8)中，A17 為-O-、-S-或-NH-，但以-O-為佳。In formula (8), A 17 is -O-, -S- or -NH-, but -O- is preferred.

式(8)中，A18 為碳數6～20的(n+1)價芳香族烴基，該芳香族烴基為從碳數6～20的芳香族烴化合物的芳香環上除去(n+1)個氫原子而得到的基。如此之芳香族烴化合物方面，可舉例如苯、甲苯、二甲苯、聯苯、萘、蒽、芘等。此等中，A18 方面，以萘或蒽所衍生的基為佳、萘所衍生的基更佳。In formula (8), A 18 is a (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbons, and the aromatic hydrocarbon group is removed from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbons (n+1 ) A hydrogen atom. Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene. Among these, A 18 is preferably a group derived from naphthalene or anthracene, and a group derived from naphthalene is more preferable.

式(8)中，Rs14 ～Rs17 各自獨立，為氫原子、或直鏈狀或者分枝狀的碳數1～20的1價脂肪族烴基。Rs14 ～Rs17 所表示之1價脂肪族烴基方面，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、s-丁基、t-丁基、n-戊基、環戊基、n-己基、環己基、n-庚基、n-辛基、n-壬基、n-癸基、n-十一基、n-十二基等之碳數1～20的烷基；乙烯基、1-丙烯基、2-丙烯基、異丙烯基、1-甲基-2-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、己烯基等之碳數2～20的烯基等。此等中，以碳數1～20的烷基為佳、碳數1～10的烷基更佳、碳數1～8的烷基再佳。In the formula (8), R s14 ~ R s17 each independently represent a hydrogen atom, a linear or branched carbon atoms or a monovalent aliphatic hydrocarbon group having 1 to 20. A monovalent aliphatic hydrocarbon group R s14 ~ R s17 aspect represented by the includes, for example, methyl, ethyl, N- propyl, isopropyl, N- butyl, isobutyl, butyl S-, T-butoxy Base, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, etc. The alkyl group with 1 to 20 carbons; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3 -C2-20 alkenyl groups such as butenyl and hexenyl. Among these, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 8 carbon atoms is even more preferred.

式(8)中，Rs18 為直鏈狀或者分枝狀的碳數1～20的1價脂肪族烴基、或-ORs19 。Rs19 為可經取代的碳數2～20的1價烴基。In the formula (8), R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or -OR s19 . R s19 is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbon atoms.

Rs18 所表示之直鏈狀或分枝狀的碳數1～20的1價脂肪族烴基方面，可舉例如與Rs14 ～Rs17 的說明中例示者相同者。Rs18 為1價脂肪族烴基時，Rs18 以碳數1～20的烷基為佳、碳數1～10的烷基更佳、碳數1～8的烷基再佳。A linear or branched carbon atoms of the monovalent aliphatic hydrocarbon group having 1 to 20 represented aspect of R s18, as shown by way of example may be the same as those described in R s14 ~ R s17 in Fig. When R s18 is a monovalent aliphatic hydrocarbon group, R s18 is preferably an alkyl group having 1 to 20 carbons, more preferably an alkyl group having 1 to 10 carbons, and even more preferably an alkyl group having 1 to 8 carbons.

Rs19 所表示之碳數2～20的1價烴基方面，作為Rs14 ～Rs17 所表示之1價脂肪族烴基例示者中甲基以外者之外，可舉例如苯基、萘基、菲基等之芳基等。此等中，Rs19 方面，以碳數2～4之直鏈烷基或苯基為佳。Monovalent hydrocarbon group having a carbon number of 2 to 20 represented by the aspect of R s19, was used as the monovalent aliphatic hydrocarbon group exemplified by the persons other than methyl R s14 ~ R s17 of represented includes, for example, phenyl, naphthyl, phenanthrene The aryl group and so on. Among these, R s19 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group.

又，前述1價烴基可具有的取代基方面，可舉例如氟原子、碳數1～4的烷氧基、硝基、氰基等。In addition, examples of the substituent that the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, and a cyano group.

適宜之芳基磺酸酯化合物的具體例方面，可舉例如以下所示者，但不限於此等。Specific examples of suitable arylsulfonate compounds include those shown below, but are not limited to these.

Figure 02_image023
Figure 02_image023

本發明之電荷輸送性塗漆含有摻雜劑時，其含量因摻雜劑的種類、期望的電荷輸送性等而異，故一般無法指定，但相對電荷輸送性物質1而言，質量比通常在0.01～10的範圍內。When the charge-transporting paint of the present invention contains a dopant, its content varies depending on the type of dopant, the desired charge-transporting properties, etc., so generally cannot be specified, but compared to the charge-transporting material 1, the mass is more In the range of 0.01-10.

本發明之電荷輸送性塗漆以得到的電荷輸送性薄膜的膜物性的調整等之目的，可進而含有有機矽烷化合物。前述有機矽烷化合物方面，可舉例如二烷氧基矽烷化合物、三烷氧基矽烷化合物或四烷氧基矽烷化合物。特別係有機矽烷化合物方面，以二烷氧基矽烷化合物或三烷氧基矽烷化合物為佳、三烷氧基矽烷化合物更佳。有機矽烷化合物可1種單獨或2種以上組合使用。The charge-transporting paint of the present invention may further contain an organosilane compound for the purpose of adjusting the film properties of the obtained charge-transporting film. With respect to the aforementioned organosilane compound, for example, a dialkoxysilane compound, a trialkoxysilane compound, or a tetraalkoxysilane compound can be mentioned. In terms of organosilane compounds in particular, dialkoxysilane compounds or trialkoxysilane compounds are preferred, and trialkoxysilane compounds are more preferred. The organosilane compounds can be used alone or in combination of two or more.

有機矽烷化合物的含量，相對於電荷輸送性物質及摻雜劑的總質量，通常為0.1～50質量%左右，但考量抑制得到的薄膜的電荷輸送性的降低，且提高對以接觸由本發明之電荷輸送性薄膜所構成的電洞注入層之方式層合於陽極相反側的層(例如電洞輸送層或發光層)的電洞注入能力，較佳為0.5～40質量%左右、更佳為0.8～30質量%左右、再佳為1～20質量%左右。The content of the organosilane compound is usually about 0.1-50% by mass relative to the total mass of the charge-transporting substance and the dopant. However, it is considered that the reduction in the charge transportability of the obtained film is suppressed, and the contact is improved by the present invention. The hole injection layer formed by the charge transporting thin film is laminated on the opposite side of the anode (for example, the hole transport layer or the light emitting layer). The hole injection ability is preferably about 0.5-40% by mass, more preferably About 0.8 to 30% by mass, more preferably about 1 to 20% by mass.

電荷輸送性塗漆的調製方法雖不特別限制，可舉例如將(A)成分及(C)成分等以任意順序或同時加入於溶劑之方法。又，有機溶劑為複數時，可首先將(A)成分、(C)成分等溶於1種溶劑，再於其加入其他溶劑、或於複數有機溶劑的混合溶劑將(A)成分、(C)成分等依序或同時溶解。Although the preparation method of a charge-transporting paint is not specifically limited, the method of adding (A) component, (C) component, etc. to a solvent in arbitrary order or simultaneously is mentioned, for example. In addition, when there are plural organic solvents, first dissolve (A) component, (C) component, etc. in one solvent, and then add another solvent to it, or mix (A) component, (C) in a mixed solvent of plural organic solvents. ) The ingredients are dissolved sequentially or simultaneously.

本發明之電荷輸送性塗漆由再現性佳地得到平坦性更高的薄膜觀點，以將(A)成分、(C)成分等溶於有機溶劑後，使用亞微米級的過濾器等進行過濾為佳。The charge-transporting paint of the present invention is based on the viewpoint of obtaining a film with higher flatness with good reproducibility. After dissolving the components (A) and (C) in an organic solvent, they are filtered using a sub-micron filter. Better.

本發明之電荷輸送性塗漆之固形分濃度，由一邊抑制電荷輸送性物質之析出一邊確保充分的膜厚觀點，通常為0.1～20質量%左右、較佳為0.5～10質量%。又，固形分係指塗漆所含有的成分中溶劑以外的成分。The solid content concentration of the charge-transporting paint of the present invention, from the viewpoint of ensuring a sufficient film thickness while suppressing the precipitation of the charge-transporting substance, is usually about 0.1-20% by mass, preferably 0.5-10% by mass. In addition, the solid content refers to components other than the solvent among the components contained in the paint.

本發明之電荷輸送性塗漆的黏度，通常在25℃為1～50mPa･s。又，本發明之電荷輸送性塗漆的表面張力，通常在25℃為20～50mN/m。又，黏度為以東機產業(股)製TVE-25形黏度計測定之值。表面張力為以協和界面科學(股)製自動表面張力計CBVP-Z型測定之值。塗漆的黏度與表面張力，可考量期望的膜厚等之各種要素，藉由變更前述溶劑的種類或彼等之比率、固形分濃度等來調整。The viscosity of the charge transport paint of the present invention is usually 1-50mPa･s at 25°C. In addition, the surface tension of the charge-transporting paint of the present invention is usually 20-50 mN/m at 25°C. In addition, the viscosity is a value measured with a TVE-25 viscometer manufactured by Toki Sangyo Co., Ltd. The surface tension is the value measured with the automatic surface tensiometer CBVP-Z manufactured by Kyowa Interface Science (Stock). The viscosity and surface tension of the paint can be adjusted by considering various factors such as the desired film thickness, and by changing the types of solvents, their ratios, and solid content.

[電荷輸送性薄膜] 本發明之電荷輸送性薄膜可藉由將本發明之電荷輸送性塗漆塗佈於基材上，進行燒成來形成。[Charge Transporting Film] The charge-transporting film of the present invention can be formed by coating the charge-transporting paint of the present invention on a substrate and firing it.

塗漆的塗佈方法方面，雖不特別限制，可舉例如浸漬法、旋轉塗佈法、轉印印刷法、滾筒塗佈法、刷毛塗佈法、噴墨法、噴霧法、狹縫塗佈法等。以因應塗佈方法調節塗漆的黏度及表面張力為佳。The coating method of the lacquer is not particularly limited, for example, dipping method, spin coating method, transfer printing method, roller coating method, brush coating method, inkjet method, spray method, slit coating Law etc. It is better to adjust the viscosity and surface tension of the paint according to the coating method.

又，塗佈後的電荷輸送性塗漆的燒成環境亦不特別限制，不僅大氣環境，在氮等之惰性氣體或真空中亦可得到具有均勻的成膜面及高電荷輸送性的薄膜。因一起使用的摻雜劑的種類，而將塗漆在大氣環境下進行燒成，有再現性佳地得到具有電荷輸送性的薄膜之情形。In addition, the firing environment of the charge-transporting paint after application is not particularly limited, and not only the atmospheric environment, but also in an inert gas such as nitrogen or vacuum, a thin film having a uniform film-forming surface and high charge-transporting properties can be obtained. Depending on the type of dopant used together, the lacquer is fired in an atmospheric environment to obtain a film with charge transport properties with good reproducibility.

燒成溫度考量得到的薄膜的用途、賦予得到的薄膜之電荷輸送性的程度、溶劑的種類或沸點等，在100～260℃左右之範圍內適宜設定，並將得到的薄膜用作為有機EL元件的電洞注入層時，以140～250℃左右為佳、145～240℃左右更佳，但在本發明之電荷輸送性塗漆，即使200℃以下之低溫燒成，亦能得到具有良好的電荷輸送性的薄膜。又，燒成之際，以表現更高均勻成膜性、使反應在基材上進行之目的，可設置2階段以上之溫度變化，加熱例如使用加熱板或烤箱等適當的機器進行即可。The firing temperature considers the purpose of the film obtained, the degree of charge transportability imparted to the film obtained, the type of solvent or the boiling point, etc., are appropriately set within the range of about 100 to 260°C, and the obtained film is used as an organic EL element In the case of the hole injection layer, it is preferably about 140-250°C, more preferably about 145-240°C. However, the charge-transporting paint of the present invention can be fired at a low temperature below 200°C. Charge-transporting film. In addition, at the time of firing, for the purpose of exhibiting higher uniform film-forming properties and allowing the reaction to proceed on the substrate, two or more temperature changes may be provided, and heating may be performed using an appropriate machine such as a hot plate or an oven.

電荷輸送性薄膜的膜厚，雖不特別限制，用作為有機EL元件的電洞注入層、電洞輸送層或電洞注入輸送層時，以5～300nm為佳。改變膜厚之方法方面，有改變塗漆中之固形分濃度、改變塗佈時基板上的液量等之方法。Although the film thickness of the charge transporting thin film is not particularly limited, when it is used as a hole injection layer, a hole transport layer, or a hole injection and transport layer of an organic EL device, it is preferably 5 to 300 nm. In terms of the method of changing the film thickness, there are methods such as changing the solid content concentration in the paint and changing the amount of liquid on the substrate during coating.

以上說明的本發明之電荷輸送性薄膜，在400nn～800nm的波長區域的平均值，顯示1.6以上之折射率(n)與0.020以下的消衰係數(k)，但某態樣中，顯示1.65以上之折射率，另態樣中，顯示1.70以上之折射率，又，某態樣中，顯示0.010以下的消衰係數(k)，另某態樣中，顯示0.005以下的消衰係數(k)。The charge transporting film of the present invention described above shows an average refractive index (n) of 1.6 or more and an attenuation coefficient (k) of 0.020 or less in the wavelength region of 400nm to 800nm, but in a certain aspect, it shows 1.65 The above refractive index, in another aspect, shows a refractive index above 1.70, and in a certain aspect, shows an attenuation coefficient (k) below 0.010, and in another aspect, shows an attenuation coefficient (k) below 0.005 ).

[有機EL元件] 本發明之有機EL元件為具有一對電極，且於此等電極間具有由本發明之電荷輸送性薄膜所構成的機能層者。[Organic EL element] The organic EL device of the present invention has a pair of electrodes, and a functional layer composed of the charge transport film of the present invention is provided between these electrodes.

有機EL元件的代表的構成方面，可舉例如以下的(a)～(f)，但不限於此等。又，下述構成中，因應必要在發光層與陽極間可設置電子阻隔層等，在發光層與陰極間可設置電洞(hole)阻隔層等。又，電洞注入層、電洞輸送層或者電洞注入輸送層可兼具作為電子阻隔層等之機能，電子注入層、電子輸送層或電子注入輸送層可兼具作為電洞阻隔層等之機能。更且亦可因應必要在各層間設置任意之機能層。 (a)陽極/電洞注入層/電洞輸送層/發光層/電子輸送層/電子注入層/陰極 (b)陽極/電洞注入層/電洞輸送層/發光層/電子注入輸送層/陰極 (c)陽極/電洞注入輸送層/發光層/電子輸送層/電子注入層/陰極 (d)陽極/電洞注入輸送層/發光層/電子注入輸送層/陰極 (e)陽極/電洞注入層/電洞輸送層/發光層/陰極 (f)陽極/電洞注入輸送層/發光層/陰極The representative structure of the organic EL element includes, for example, the following (a) to (f), but it is not limited to these. In addition, in the following configuration, an electron barrier layer or the like may be provided between the light-emitting layer and the anode, and a hole barrier layer or the like may be provided between the light-emitting layer and the cathode. In addition, the hole injection layer, the hole transport layer, or the hole injection and transport layer can also serve as an electron barrier layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer can also serve as a hole barrier layer, etc. function. Moreover, any functional layer can be set between each layer as necessary. (a) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (b) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection and transport layer / cathode (c) Anode/hole injection transport layer/light emitting layer/electron transport layer/electron injection layer/cathode (d) Anode/hole injection and transport layer/light emitting layer/electron injection and transport layer/cathode (e) Anode/hole injection layer/hole transport layer/light-emitting layer/cathode (f) Anode/hole injection transport layer/light emitting layer/cathode

「電洞注入層」、「電洞輸送層」及「電洞注入輸送層」係指形成於發光層與陽極間之層，且具有將電洞從陽極輸送至發光層之機能者。在發光層與陽極間，電洞輸送性材料之層僅設置1層時，其為「電洞注入輸送層」，在發光層與陽極間，電洞輸送性材料之層設置2層以上時，接近陽極的層為「電洞注入層」，其以外的層為「電洞輸送層」。尤其，電洞注入(輸送)層，使用不僅來自陽極的電洞接受性，且至電洞輸送(發光)層的電洞注入性亦優異的薄膜。The "hole injection layer", "hole transport layer" and "hole injection transport layer" refer to layers formed between the light-emitting layer and the anode, and have the function of transporting holes from the anode to the light-emitting layer. When only one layer of hole transporting material is provided between the light-emitting layer and the anode, it is a "hole injection and transport layer". When two or more layers of hole transporting material are provided between the light-emitting layer and the anode, The layer close to the anode is the "hole injection layer", and the other layer is the "hole transport layer". In particular, as the hole injection (transport) layer, a thin film that is excellent not only in hole acceptability from the anode, but also in hole injection into the hole transport (luminescent) layer is used.

「電子注入層」、「電子輸送層」及「電子注入輸送層」係指形成於發光層與陰極間之層，且具有將電子從陰極輸送至發光層之機能者。在發光層與陰極間，電子輸送性材料之層僅設置1層時，其為「電子注入輸送層」，在發光層與陰極間，電子輸送性材料之層設置2層以上時，接近陰極的層為「電子注入層」，其以外的層為「電子輸送層」。"Electron injection layer," "electron transport layer," and "electron injection and transport layer" refer to layers formed between the light-emitting layer and the cathode, and have the function of transporting electrons from the cathode to the light-emitting layer. When only one layer of electron transport material is provided between the light-emitting layer and the cathode, it is an "electron injection and transport layer". When two or more layers of electron transport material are provided between the light-emitting layer and the cathode, it is close to the cathode The layer is the "electron injection layer", and the other layer is the "electron transport layer".

「發光層」係指具有發光機能的有機層，採用摻雜系統時，含有主體材料與摻雜劑材料。此時，主體材料主要具有促進電子與電洞的再結合，使激子局限於發光層內的機能，摻雜劑材料具有使再結合所得到的激子有效率地發光的機能。為磷光元件時，主體材料主要具有使摻雜劑所生成的激子局限於發光層內的機能。"Light-emitting layer" refers to an organic layer with light-emitting function. When a doping system is used, it contains a host material and a dopant material. At this time, the host material mainly has the function of promoting the recombination of electrons and holes and confining excitons in the light-emitting layer, and the dopant material has the function of making the excitons obtained by the recombination emit light efficiently. In the case of a phosphorescent element, the host material mainly has the function of confining excitons generated by the dopant in the light-emitting layer.

本發明之電荷輸送性薄膜在有機EL元件中，可適於用作為設置於陽極與發光層間的機能層，更宜用作為電洞注入層、電洞輸送層、電洞注入輸送層，再宜用作為電洞注入層。The charge-transporting thin film of the present invention can be suitably used as a functional layer provided between the anode and the light-emitting layer in an organic EL device, and more preferably as a hole injection layer, a hole transport layer, and a hole injection and transport layer. Used as a hole injection layer.

使用本發明之電荷輸送性塗漆，製作有機EL元件時的使用材料或製作方法方面，可舉例如下述者，但不限於此等。Examples of the materials used and the manufacturing method used when the charge-transporting paint of the present invention is used to manufacture an organic EL device include the following, but are not limited to these.

具有由本發明之電荷輸送性塗漆所得到的電荷輸送性薄膜所構成的電洞注入層的有機EL元件之製作方法的一例如下。又，電極在不對電極有負面影響之範圍，以預先進行醇、純水等之洗淨或UV臭氧處理、氧-電漿處理等之表面處理為佳。An example of a method for producing an organic EL device having a hole injection layer composed of a charge-transporting thin film obtained by the charge-transporting paint of the present invention is as follows. In addition, in the range where the electrode does not have a negative influence on the electrode, it is better to pre-wash with alcohol, pure water, etc., or surface treatment such as UV ozone treatment, oxygen-plasma treatment, etc.

在陽極基板上，藉由前述方法，使用本發明之電荷輸送性塗漆，形成電洞注入層。將其導入真空蒸鍍裝置內，依序蒸鍍電洞輸送層、發光層、電子輸送層/電洞阻隔層、電子注入層、陰極金屬。或者在該方法中，代替以蒸鍍形成電洞輸送層與發光層，而使用含有電洞輸送性高分子之電洞輸送層形成用組成物與含有發光性高分子的發光層形成用組成物，以濕製程形成此等之層。又，因應必要可在發光層與電洞輸送層間形成電子阻隔層。On the anode substrate, the charge-transporting paint of the present invention is used by the aforementioned method to form a hole injection layer. It is introduced into a vacuum evaporation device, and the hole transport layer, the light emitting layer, the electron transport layer/hole barrier layer, the electron injection layer, and the cathode metal are sequentially evaporated. Or in this method, instead of forming the hole transport layer and the light emitting layer by vapor deposition, a hole transport layer forming composition containing a hole transporting polymer and a light emitting layer forming composition containing a light emitting polymer are used , To form these layers by wet process. In addition, an electron blocking layer can be formed between the light-emitting layer and the hole transport layer if necessary.

陽極材料方面，可舉例如銦錫氧化物(ITO)、銦鋅氧化物(IZO)為代表的透明電極或鋁為代表的金屬或合金等所構成的金屬陽極，以經平坦化處理者為佳。亦可使用具有高電荷輸送性的聚噻吩衍生物或聚苯胺衍生物。又，構成金屬陽極的其他金屬方面，可舉例如金、銀、銅、銦或此等之合金等，但不限於此等。In terms of anode material, for example, a transparent electrode represented by indium tin oxide (ITO) and indium zinc oxide (IZO), or a metal anode represented by aluminum or a metal or alloy composed of metal anodes, is preferred. . Polythiophene derivatives or polyaniline derivatives having high charge transport properties can also be used. In addition, other metals constituting the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.

形成電洞輸送層的材料方面，可舉例如(三苯基胺)二聚物衍生物、[(三苯基胺)二聚物]螺二聚物、N,N’-雙(萘-1-基)-N,N’-雙(苯基)-聯苯胺(α-NPD)、4,4’,4”-參[3-甲基苯基(苯基)胺基]三苯基胺(m-MTDATA)、4,4’,4”-參[1-萘基(苯基)胺基]三苯基胺(1-TNATA)等之三芳基胺類、5,5”-雙-{4-[雙(4-甲基苯基)胺基]苯基}-2,2’:5’,2”-三聯噻吩(BMA-3T)等之寡噻吩類等。With regard to the material forming the hole transport layer, for example, (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spiro dimer, N,N'-bis(naphthalene-1) -Yl)-N,N'-bis(phenyl)-benzidine (α-NPD), 4,4',4"-[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4',4"-[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA) and other triarylamines, 5,5"-bis- {4-[Bis(4-methylphenyl)amino]phenyl}-2,2':5',2"-Trithiophene (BMA-3T) and other oligothiophenes.

形成發光層的材料方面，可舉例如於8-羥基喹啉的鋁錯合物等之金屬錯合物、10-羥基苯並[h]喹啉的金屬錯合物、雙苯乙烯基苯衍生物、雙苯乙烯基伸芳基衍生物、(2-羥基苯基)苯並噻唑的金屬錯合物、噻咯衍生物等之低分子發光材料；聚(p-伸苯基伸乙烯基)、聚[2-甲氧基-5-(2-乙基己基氧基)-1,4-伸苯基伸乙烯基]、聚(3-烷基噻吩)、聚乙烯基咔唑等之高分子化合物混合發光材料與電子移動材料的系等，但不限於此等。As for the material forming the light-emitting layer, for example, metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, and bisstyrylbenzene derivatives Low-molecular-weight luminescent materials such as bis-styrene arylene derivatives, metal complexes of (2-hydroxyphenyl) benzothiazole, silole derivatives; poly(p-phenylene ethylene), poly [2-Methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly(3-alkylthiophene), polyvinylcarbazole and other polymer compounds mixed The relationship between luminescent materials and electron mobility materials, but not limited to these.

又，以蒸鍍形成發光層時，可與發光性摻雜劑進行共蒸鍍，發光性摻雜劑方面，可舉例如參(2-苯基吡啶)銥(III)(Ir(ppy)3 )等之金屬錯合物或紅熒烯等之丁省衍生物、喹吖啶酮衍生物、苝等之縮合多環芳香族環等，但不限於此等。In addition, when the light-emitting layer is formed by vapor deposition, it can be co-evaporated with a light-emitting dopant. As for the light-emitting dopant, for example, (2-phenylpyridine)iridium(III)(Ir(ppy) 3 ) And other metal complexes, rubrene and other derivatives, quinacridone derivatives, perylene and other condensed polycyclic aromatic rings, but not limited to these.

形成電子輸送層/電洞阻隔層的材料方面，可舉例如氧基二唑衍生物、***衍生物、菲繞啉衍生物、苯基喹喔啉衍生物、苯並咪唑衍生物、嘧啶衍生物等，但不限於此等。The materials for forming the electron transport layer/hole barrier layer include, for example, oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives. Things, but not limited to these.

形成電子注入層的材料方面，可舉例如氧化鋰(Li2 O)、氧化鎂(MgO)、氧化鋁(Al2 O3 )等之金屬氧化物、氟化鋰(LiF)、氟化鈉(NaF)的金屬氟化物等，但不限於此等。In terms of materials for forming the electron injection layer, for example, metal oxides such as lithium oxide (Li 2 O), magnesium oxide (MgO), aluminum oxide (Al 2 O 3 ), lithium fluoride (LiF), sodium fluoride ( NaF), but not limited to metal fluorides, etc.

陰極材料方面，可舉例如鋁、鎂-銀合金、鋁-鋰合金等，但不限於此等。As for the cathode material, for example, aluminum, magnesium-silver alloy, aluminum-lithium alloy, etc., but not limited to these.

形成電子阻隔層的材料方面，可舉例如參(苯基吡唑)銥等，但不限於此。Regarding the material for forming the electron blocking layer, for example, ginseng (phenylpyrazole) iridium and the like, but not limited thereto.

電洞輸送性高分子方面，可舉例如聚[(9,9-二己基茀基-2,7-二基)-co-(N,N’-雙{p-丁基苯基}-1,4-二胺基伸苯基)]、聚[(9,9-二辛基茀基-2,7-二基)-co-(N,N’-雙{p-丁基苯基}-1,1’-伸聯苯基-4,4-二胺)]、聚[(9,9-雙{1’-戊烯-5’-基}茀基-2,7-二基)-co-(N,N’-雙{p-丁基苯基}-1,4-二胺基伸苯基)]、聚[N,N’-雙(4-丁基苯基)-N,N’-雙(苯基)-聯苯胺]-以聚倍半矽氧烷材料封端、聚[(9,9-二二辛基茀基-2,7-二基)-co-(4,4’-(N-(p-丁基苯基))二苯基胺)]等。For hole transporting polymers, for example, poly[(9,9-dihexyl -2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1 ,4-Diaminophenylene)], poly[(9,9-dioctylphenylenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl)- 1,1'-biphenylene-4,4-diamine)], poly[(9,9-bis{1'-pentene-5'-yl}tyl-2,7-diyl)- co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)], poly[N,N'-bis(4-butylphenyl)-N,N '-Bis(phenyl)-benzidine]-terminated with polysilsesquioxane material, poly[(9,9-dioctylphenidyl-2,7-diyl)-co-(4, 4'-(N-(p-butylphenyl))diphenylamine)] etc.

發光性高分子方面，可舉例如聚(9,9-二烷基茀)(PDAF)等之聚茀衍生物、聚(2-甲氧基-5-(2’-乙基己氧基)-1,4-伸苯基伸乙烯基)(MEH-PPV)等之聚伸苯基伸乙烯基衍生物、聚(3-烷基噻吩)(PAT)等之聚噻吩衍生物、聚乙烯基咔唑(PVCz)等。In terms of light-emitting polymers, for example, poly(9,9-dialkyl fluoride) (PDAF) and other such polypyridine derivatives, poly(2-methoxy-5-(2'-ethylhexyloxy) -1,4-Phenylene vinylene) (MEH-PPV) and other polyphenylene vinylene derivatives, poly(3-alkylthiophene) (PAT) and other polythiophene derivatives, polyvinyl carbazole (PVCz) and so on.

構成陽極與陰極及形成於此等之間的層之材料，取決於製造具備底部發光構造、還是頂部發光構造之元件而異，考量該點選擇適宜材料。The materials constituting the anode and the cathode and the layers formed between them vary depending on whether the device is manufactured with a bottom-emitting structure or a top-emitting structure, and appropriate materials are selected in consideration of this point.

通常，相對於在底部發光構造之元件，基板側使用透明陽極，從基板側取出光，在頂部發光構造之元件，使用由金屬所構成的反射陽極，從與基板相反方向的透明電極(陰極)側取出光。因此，例如提及陽極材料，分別在製造底部發光構造之元件時，使用ITO等之透明陽極，製造頂部發光構造之元件時，使用Al/Nd等之反射陽極。Generally, in contrast to the bottom emitting structure of the element, the substrate side uses a transparent anode to extract light from the substrate side, and the top emitting structure of the element uses a reflective anode made of metal, from the transparent electrode (cathode) opposite to the substrate. Take out the light side. Therefore, for example, referring to anode materials, transparent anodes such as ITO are used when manufacturing bottom-emitting devices, and reflective anodes such as Al/Nd are used when manufacturing top-emitting devices.

本發明之有機EL元件為了防止特性惡化，可依常規方法，因應必要與捕水劑等一起密封。In order to prevent the deterioration of the characteristics of the organic EL device of the present invention, it can be sealed with a water-trapping agent or the like according to a conventional method as necessary.

本發明之電荷輸送性塗漆如前述，宜用於有機EL元件的機能層的形成，其他亦可利用於有機光電轉換元件、有機薄膜太陽能電池、有機鈣鈦礦光電轉換元件、有機積體電路、有機電場效果電晶體、有機薄膜電晶體、有機發光電晶體、有機光學檢查器、有機感光體、有機電場消光元件、發光電子化學電池、量子點發光二極體、量子雷射、有機雷射二極體及有機等離子體發光元件等之電子元件之機能層的形成。The charge-transporting paint of the present invention is suitable for the formation of the functional layer of organic EL devices as mentioned above. Others can also be used for organic photoelectric conversion devices, organic thin film solar cells, organic perovskite photoelectric conversion devices, and organic integrated circuits. , Organic electric field effect transistors, organic thin film transistors, organic light-emitting transistors, organic optical inspectors, organic photoreceptors, organic electric field extinction elements, light-emitting electronic chemical batteries, quantum dot light-emitting diodes, quantum lasers, organic lasers Formation of functional layers of electronic components such as diodes and organic plasma light-emitting devices.

[實施例][Example]

以下舉實施例及比較例，將本發明更具體說明，但本發明不限於下述實施例。又，使用之裝置如下。 (1)1 H-NMR、19 F-NMR:JEOL(股)製、核磁共振裝置AL-300 (2)基板洗淨:長州產業(股)製、基板洗淨裝置(減壓電漿方式) (3)塗漆的塗佈:MIKASA(股)製、旋轉塗佈機MS-A100 (4)膜厚測定:(股)小坂研究所製、微細形狀測定機Surfcorder ET-4000 (5)膜的表面觀察:LASERTEC公司製、共焦點雷射顯微鏡、同步掃描型雷射顯微鏡1LM21D (6)EL元件之製作:長州產業(股)製、多機能蒸鍍裝置系統C-E2L1G1-N (7)EL元件的亮度等之測定:(股)EHC製、多頻道IVL測定裝置 (8)EL元件的壽命測定(亮度半衰期測定):(股)EHC製、有機EL亮度壽命評估系統PEL-105S (9)LDI-MS:Bruker公司製AutoFlex (10)折射率及消衰係數的測定:JA Woollam JAPAN製、多入射角光譜式橢圓儀VASE (11)重量平均分子量(Mw)及數平均分子量(Mn)測定:(股)島津製作所製(管柱:Shodex GPC KF-805L+KF-804L、管柱溫度；40℃、偵測器:UV偵測器(254nm)、溶離液:THF、管柱流速:1.0mL/min)Examples and comparative examples are given below to illustrate the present invention in more detail, but the present invention is not limited to the following examples. Also, the devices used are as follows. (1) 1 H-NMR, 19 F-NMR: JEOL Co., Ltd., nuclear magnetic resonance device AL-300 (2) Substrate cleaning: Choju Sangyo Co., Ltd., substrate cleaning device (decompression plasma method) (3) Coating of paint: MIKASA Co., Ltd., spin coater MS-A100 (4) Film thickness measurement: Co., Ltd. Kosaka Research Institute, Micro shape measuring machine Surfcorder ET-4000 (5) Film Surface observation: LASERTEC Co., Ltd., confocal laser microscope, synchronous scanning laser microscope 1LM21D (6) Production of EL elements: Changzhou Industrial Co., Ltd., multi-function evaporation device system C-E2L1G1-N (7) EL Measurement of element brightness, etc.: (share) EHC system, multi-channel IVL measuring device (8) EL element lifetime measurement (luminance half-life measurement): (share) EHC system, organic EL brightness lifetime evaluation system PEL-105S (9) LDI-MS: AutoFlex manufactured by Bruker (10) Refractive index and decay coefficient measurement: JA Woollam JAPAN, multiple incident angle spectroscopic ellipsometer VASE (11) Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) : (Stock) manufactured by Shimadzu Corporation (column: Shodex GPC KF-805L+KF-804L, column temperature; 40℃, detector: UV detector (254nm), eluent: THF, column flow rate: 1.0 mL/min)

[實施例1]聚合物P-1的合成 (1)4’-(3-溴-9H-咔唑-9-基)-N,N-二苯基-[1,1’-聯苯基]-4-胺的合成

Figure 02_image025
[Example 1] Synthesis of polymer P-1 (1) 4'-(3-bromo-9H-carbazol-9-yl)-N,N-diphenyl-[1,1'-biphenyl ]-4-amine synthesis
Figure 02_image025

將3-溴-9-(4-碘苯基)-9H-咔唑4.0g、N,N-二苯基-4-(4,4,5,5-四甲基-1,3,2-二氧雜硼烷-2-基)苯胺3.5g、肆三苯基膦鈀0.21g、N-甲基-N,N,N-三辛基銨氯化物1.1g、四氫呋喃40mL及2mol/L碳酸鉀水溶液34mL置入反應容器，進行氮取代後，在60℃進行8小時攪拌。回到室溫後，加入甲苯及離子交換水進行分液。使有機相以硫酸鈉乾燥後，於將溶劑減壓餾去而得到的殘渣，加入1,4-二噁烷40g，加熱至80℃後，放冷至室溫。加入甲醇40mL，進而在室溫進行3小時攪拌，進行過濾、乾燥，得到目的之4’-(3-溴-9H-咔唑-9-基)-N,N-二苯基-[1,1’-聯苯基]-4-胺3.6g(產量:71%)。1 H-NMR (500MHz, CDCl3 ) δ[ppm]: 8.25(d, J=1.5Hz, 1H)，8.09(d, J=8.0Hz, 1H), 7.78(dd, J=8.0, 1.5Hz, 2H), 7.54-7.57(m, 4H), 7.49(dd, J=8.5, 2.0Hz, 1H), 7.44(d, J=3.5Hz, 2H), 7.28-7.33(m, 6H), 7.15-7.19(m, 6H), 7.06(t, J=7.5, 2H)。Mix 3-bromo-9-(4-iodophenyl)-9H-carbazole 4.0g, N,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2 -Dioxaborane-2-yl)aniline 3.5g, triphenylphosphine palladium 0.21g, N-methyl-N,N,N-trioctylammonium chloride 1.1g, tetrahydrofuran 40mL and 2mol/L 34 mL of potassium carbonate aqueous solution was put into the reaction vessel, and after nitrogen substitution, it was stirred at 60°C for 8 hours. After returning to room temperature, toluene and ion-exchanged water were added for liquid separation. After the organic phase was dried with sodium sulfate, 40 g of 1,4-dioxane was added to the residue obtained by distilling off the solvent under reduced pressure, and the mixture was heated to 80°C and then allowed to cool to room temperature. 40 mL of methanol was added, followed by stirring at room temperature for 3 hours, filtration and drying to obtain the desired 4'-(3-bromo-9H-carbazol-9-yl)-N,N-diphenyl-[1, 1'-biphenyl]-4-amine 3.6 g (yield: 71%). 1 H-NMR (500MHz, CDCl 3 ) δ[ppm]: 8.25(d, J=1.5Hz, 1H), 8.09(d, J=8.0Hz, 1H), 7.78(dd, J=8.0, 1.5Hz, 2H), 7.54-7.57(m, 4H), 7.49(dd, J=8.5, 2.0Hz, 1H), 7.44(d, J=3.5Hz, 2H), 7.28-7.33(m, 6H), 7.15-7.19 (m, 6H), 7.06(t, J=7.5, 2H).

(2)N,N-二苯基-4’-(3-乙烯基-9H-咔唑-9-基)-[1,1’-聯苯基]-4-胺的合成

Figure 02_image027
(2) Synthesis of N,N-diphenyl-4'-(3-vinyl-9H-carbazol-9-yl)-[1,1'-biphenyl]-4-amine
Figure 02_image027

將4’-(3-溴-9H-咔唑-9-基)-N,N-二苯基-[1,1’-聯苯基]-4-胺3.2g及[1,1’-雙(二苯基膦基)二茂鐵]鈀二氯化物0.23g置入反應容器後，進行氮取代。加入四氫呋喃50mL，加入乙烯基鎂氯化物的四氫呋喃溶液(濃度1.45mol/L)，在60℃進行4小時加熱攪拌。令反應液回到室溫後，加入飽和食鹽水、氯仿進行分液。使有機相以硫酸鈉乾燥後，將溶劑減壓餾去。將得到的濃縮殘渣以管柱層析法(展開溶劑:氯仿/n-己烷=80/20)精製，得到目的之N,N-二苯基-4’-(3-乙烯基-9H-咔唑-9-基)-[1,1’-聯苯基]-4-胺2.6g(產量:89%)。1 H-NMR(500MHz, CDCl3 ) δ[ppm]: 8.14(s, 1H), 8.12(d, J=7.5Hz, 1H), 7.71(d, J=8.5, 2H), 7.47-7.53(m, 5H), 7.35-7.42(m, 3H), 7.24-7.27(m, 4H), 7.13-7.17(m, 7H), 7.03(t, J=7.5, 2H), 6.89(dd, J=17.5, 11Hz, 1H), 5.76(d, J=17.5Hz, 1H), 5.19(d, J=11Hz, 1H)。4'-(3-bromo-9H-carbazol-9-yl)-N,N-diphenyl-[1,1'-biphenyl]-4-amine 3.2g and [1,1'- After 0.23 g of bis(diphenylphosphino)ferrocene]palladium dichloride was placed in the reaction vessel, it was substituted with nitrogen. 50 mL of tetrahydrofuran was added, a tetrahydrofuran solution of vinyl magnesium chloride (concentration 1.45 mol/L) was added, and heating and stirring were performed at 60° C. for 4 hours. After the reaction solution was returned to room temperature, saturated brine and chloroform were added for liquid separation. After drying the organic phase with sodium sulfate, the solvent was distilled off under reduced pressure. The obtained concentrated residue was purified by column chromatography (developing solvent: chloroform/n-hexane=80/20) to obtain the desired N,N-diphenyl-4'-(3-vinyl-9H- Carbazol-9-yl)-[1,1'-biphenyl]-4-amine 2.6 g (yield: 89%). 1 H-NMR(500MHz, CDCl 3 ) δ[ppm]: 8.14(s, 1H), 8.12(d, J=7.5Hz, 1H), 7.71(d, J=8.5, 2H), 7.47-7.53(m , 5H), 7.35-7.42(m, 3H), 7.24-7.27(m, 4H), 7.13-7.17(m, 7H), 7.03(t, J=7.5, 2H), 6.89(dd, J=17.5, 11Hz, 1H), 5.76(d, J=17.5Hz, 1H), 5.19(d, J=11Hz, 1H).

(3)聚合物P-1的合成

Figure 02_image029
(3) Synthesis of polymer P-1
Figure 02_image029

將N,N-二苯基-4’-(3-乙烯基-9H-咔唑-9-基)-[1,1’-聯苯基]-4-胺2.5g、AIBN0.041g及甲苯15mL置入反應容器，進行氮取代後，在100℃進行20小時攪拌。放冷至室溫後，於反應液中加入甲苯15mL，將得到的溶液滴下於甲醇200mL中。在室溫進行攪拌後，進行過濾、乾燥，得到目的之聚合物P-1 2.3g(產量:93%)。GPC測定的結果，Mn=6,700、Mw=30,900。Combine 2.5 g of N,N-diphenyl-4'-(3-vinyl-9H-carbazol-9-yl)-[1,1'-biphenyl]-4-amine, AIBN0.041g and toluene 15 mL was put into the reaction vessel, and after nitrogen substitution, stirring was performed at 100°C for 20 hours. After allowing to cool to room temperature, 15 mL of toluene was added to the reaction solution, and the resulting solution was dropped into 200 mL of methanol. After stirring at room temperature, filtration and drying were performed to obtain 2.3 g of the target polymer P-1 (yield: 93%). As a result of GPC measurement, Mn=6,700 and Mw=30,900.

[實施例2]電荷輸送性塗漆的調製 於聚合物P-1 219mg及4-異丙基-4’-甲基二苯基錪肆(五氟苯基)硼酸酯(東京化成工業(股)製)44mg的混合物中，加入3-苯氧基甲苯2.5g及4-甲氧基甲苯2.5g，在室溫攪拌使其溶解，將得到的溶液以孔徑0.2μm的注射式過濾器進行過濾，得到電荷輸送性塗漆。[Example 2] Preparation of charge transport paint To a mixture of 219 mg of polymer P-1 and 44 mg of 4-isopropyl-4'-methyldiphenyl bis(pentafluorophenyl) borate (manufactured by Tokyo Chemical Industry Co., Ltd.), add 3- 2.5 g of phenoxytoluene and 2.5 g of 4-methoxytoluene were stirred at room temperature to dissolve, and the resulting solution was filtered with a syringe filter with a pore size of 0.2 μm to obtain a charge-transporting paint.

[實施例3]折射率(n)及消衰係數(k)的評估 將實施例2所得到的塗漆使用旋轉塗佈機，塗佈於石英基板後，大氣環境下、在150℃進行10分鐘燒成，在石英基板上形成70nm的均勻薄膜。使用附該薄膜的石英基板，以多入射角光譜式橢圓儀進行n值及k值的測定。結果如表1。[Example 3] Evaluation of refractive index (n) and attenuation coefficient (k) The paint obtained in Example 2 was applied to a quartz substrate using a spin coater, and then fired at 150°C for 10 minutes in an atmospheric environment to form a uniform thin film of 70 nm on the quartz substrate. Using the quartz substrate with the film, the n value and k value were measured with a multi-incident angle spectroscopic ellipsometer. The results are shown in Table 1.

Figure 02_image031
Figure 02_image031

如表1所示，本發明之電荷輸送性薄膜，折射率為1.6以上之高值，消衰係數為0.020之低值。As shown in Table 1, the charge-transporting film of the present invention has a high refractive index of 1.6 or more and a low attenuation coefficient of 0.020.

[實施例4]有機EL元件之製作及特性評估 將實施例2所得到的塗漆使用旋轉塗佈機，塗佈於ITO基板後，大氣環境下、在150℃進行10分鐘燒成，於ITO基板上形成膜厚70nm的薄膜。ITO基板方面，使用ITO在表面上以膜厚150nm圖型化的25mm×25mm×0.7t的玻璃基板，使用前以O2 電漿洗淨裝置(150W、30秒鐘)將表面上的雜質除去。 接著對形成有薄膜的ITO基板，使用蒸鍍裝置(真空度1.0×10-5 Pa)，使α-NPD以0.2nm/秒成膜95nm。接著，使關東化學(股)製的電子嵌段材料HTEB-01成膜10nm。接著將新日鐵住金化學(股)製的發光層主體材料NS60與發光層摻雜劑材料Ir(ppy)3 進行共蒸鍍。共蒸鍍以Ir(ppy)3 濃度成為6%之方式控制蒸鍍速度，層合40nm。接著依序層合Alq3 、氟化鋰及鋁的薄膜，得到有機EL元件。此際，蒸鍍速度以Alq3 及鋁為0.2nm/秒，氟化鋰為0.02nm/秒之條件各自進行，膜厚各自為20nm、0.5nm及80nm。 又，為了防止空氣中之氧、水等之影響所致之特性劣化，有機EL元件以密封基板密封後，評估其特性。密封用以下的過程進行。在氧濃度2ppm以下、露點-76℃以下的氮環境中，將有機EL元件收納於密封基板間，使密封基板以接著劑((股)MORESCO製、Moresco Moisture cut WB90US (P))貼合。此時，將捕水劑(dynic(股)製HD-071010W-40)與有機EL元件一起收納於密封基板內。對貼合的密封基板照射UV光(波長:365nm、照射量:6,000mJ/cm2 )後，在80℃、1小時，進行退火處理使接著劑硬化。[Example 4] Production and characteristic evaluation of organic EL elements. The paint obtained in Example 2 was applied to an ITO substrate using a spin coater, and then fired at 150°C for 10 minutes in an atmospheric environment. A film with a thickness of 70 nm is formed on the substrate. For the ITO substrate, a 25mm×25mm×0.7t glass substrate patterned with a film thickness of 150nm on the surface of ITO is used, and the impurities on the surface are removed with an O 2 plasma cleaning device (150W, 30 seconds) before use. . Next, on the ITO substrate on which the thin film was formed, using a vapor deposition apparatus (vacuum degree of 1.0×10 -5 Pa), α-NPD was formed into a film of 95 nm at 0.2 nm/sec. Next, an electronic block material HTEB-01 manufactured by Kanto Chemical Co., Ltd. was formed into a film of 10 nm. Next, the light-emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and the light-emitting layer dopant material Ir(ppy) 3 were co-evaporated. For co-evaporation, the evaporation rate was controlled so that the concentration of Ir(ppy) 3 became 6%, and the layering was 40 nm. Then, thin films of Alq 3 , lithium fluoride, and aluminum are sequentially laminated to obtain an organic EL device. At this time, the vapor deposition rate was 0.2 nm/sec for Alq 3 and aluminum, and 0.02 nm/sec for lithium fluoride, and the film thickness was 20 nm, 0.5 nm, and 80 nm, respectively. In addition, in order to prevent the degradation of characteristics caused by the influence of oxygen and water in the air, the organic EL element was sealed with a sealing substrate, and its characteristics were evaluated. The sealing is performed by the following process. In a nitrogen environment with an oxygen concentration of 2 ppm or less and a dew point of -76°C or less, the organic EL element was stored between the sealing substrates, and the sealing substrates were bonded with an adhesive (manufactured by MORESCO, Moresco Moisture cut WB90US (P)). At this time, a water-trapping agent (HD-071010W-40 manufactured by Dynanic Co., Ltd.) was housed in the sealing substrate together with the organic EL element. After irradiating the bonded sealing substrate with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ/cm 2 ), annealing was performed at 80° C. for 1 hour to harden the adhesive.

對得到的有機EL元件，測定使在5,000cd/m2 發光時之驅動電壓、電流密度、電流效率、發光效率、外部發光量子產量(EQE)、及亮度的半衰期(初期亮度5,000 cd/m2 到達一半所需時間)。結果如表2。The organic EL device obtained was measured in the so 5,000cd / m 2 when the light emission driving voltage, current density, current efficiency, luminous efficiency, external quantum yield of light emission (EQE of), and luminance half life (initial luminance 5,000 cd / m 2 Half the time required). The results are shown in Table 2.

Figure 02_image033
Figure 02_image033

如表2所示，具備本發明之電荷輸送性薄膜的EL元件適合驅動。As shown in Table 2, the EL element provided with the charge transport film of the present invention is suitable for driving.

Claims (12)

一種聚合物，其係含有下述式(1)所表示之重複單位，
Figure 03_image001
(式中，RA 為氫原子或甲基，X為單鍵或亞甲基，R1 ～R11 各自獨立，為氫原子、鹵素原子、硝基或者氰基、或可被鹵素原子、硝基或者氰基取代的碳數1～20的烷基、碳數1～20的烷氧基、碳數6～20的芳基、碳數6～20的芳基氧基、碳數2～20的雜芳基或者碳數2～20的雜芳基氧基，ArT 為經二(碳數6～20的芳基)胺基取代的苯基，m為0～2的整數)。A polymer containing a repeating unit represented by the following formula (1),
Figure 03_image001
(In the formula, R A is a hydrogen atom or a methyl group, X is a single bond or a methylene group, and R 1 to R 11 are independently hydrogen atom, halogen atom, nitro group or cyano group, or can be substituted by halogen atom, nitro Alkyl group or cyano substituted alkyl group having 1 to 20 carbons, alkoxy group having 1 to 20 carbons, aryl group having 6 to 20 carbons, aryloxy group having 6 to 20 carbons, 2 to 20 carbons A heteroaryl group or a heteroaryloxy group having 2 to 20 carbons, Ar T is a phenyl group substituted with a di(aryl group having 6 to 20 carbons) amino group, and m is an integer of 0 to 2). 如請求項1之聚合物，其中X為單鍵。Such as the polymer of claim 1, wherein X is a single bond. 如請求項1或2之聚合物，其中R1 ～R11 為氫原子。The polymer of claim 1 or 2, wherein R 1 to R 11 are hydrogen atoms. 如請求項1～3中任1項之聚合物，其中前述ArT 為p-(二苯基胺基)苯基、p-(1-萘基苯基胺基)苯基、p-[二(1-萘基)胺基]苯基、p-(1-萘基-2-萘基胺基)苯基、p-[二(2-萘基)胺基]苯基。The polymer according to any one of claims 1 to 3, wherein the aforementioned Ar T is p-(diphenylamino)phenyl, p-(1-naphthylphenylamino)phenyl, p-[di (1-naphthyl)amino]phenyl, p-(1-naphthyl-2-naphthylamino)phenyl, p-[bis(2-naphthyl)amino]phenyl. 如請求項1～4中任1項之聚合物，其中m為0或1。Such as the polymer of any one of claims 1 to 4, wherein m is 0 or 1. 一種電荷輸送性塗漆，其係含有(A)含有請求項1～5中任1項之聚合物的電荷輸送性物質、及(B)有機溶劑。A charge-transporting paint containing (A) a charge-transporting substance containing the polymer of any one of claims 1 to 5, and (B) an organic solvent. 如請求項6之電荷輸送性塗漆，其中進一步含有(C)摻雜劑。Such as the charge transport paint of claim 6, which further contains (C) a dopant. 如請求項7之電荷輸送性塗漆，其中前述有機溶劑含有低極性有機溶劑。The charge transport paint according to claim 7, wherein the aforementioned organic solvent contains a low-polarity organic solvent. 一種電荷輸送性薄膜，其係由請求項6～8中任1項之電荷輸送性塗漆所得到。A charge-transporting film obtained from the charge-transporting paint of any one of Claims 6 to 8. 一種有機電致發光元件，其係具備請求項9記載之電荷輸送性薄膜。An organic electroluminescence device comprising the charge-transporting thin film described in claim 9. 如請求項10之有機電致發光元件，其中前述電荷輸送性薄膜為電洞注入層或電洞輸送層。The organic electroluminescent device of claim 10, wherein the charge transporting thin film is a hole injection layer or a hole transport layer. 一種下述式(1')所表示之單體，
Figure 03_image003
(式中，RA 為氫原子或甲基，X為單鍵或亞甲基，R1 ～R11 各自獨立，為氫原子、鹵素原子、硝基或者氰基、或可被鹵素原子、硝基或者氰基取代的碳數1～20的烷基、碳數1～20的烷氧基、碳數6～20的芳基、碳數6～20的芳基氧基、碳數2～20的雜芳基或者碳數2～20的雜芳基氧基，ArT 為經二(碳數6～20的芳基)胺基取代的苯基，m為0～2的整數)。A monomer represented by the following formula (1'),
Figure 03_image003
(In the formula, R A is a hydrogen atom or a methyl group, X is a single bond or a methylene group, and R 1 to R 11 are independently hydrogen atom, halogen atom, nitro group or cyano group, or can be substituted by halogen atom, nitro Alkyl group or cyano substituted alkyl group having 1 to 20 carbons, alkoxy group having 1 to 20 carbons, aryl group having 6 to 20 carbons, aryloxy group having 6 to 20 carbons, 2 to 20 carbons A heteroaryl group or a heteroaryloxy group having 2 to 20 carbons, Ar T is a phenyl group substituted with a di(aryl group having 6 to 20 carbons) amino group, and m is an integer of 0 to 2).
TW108134987A 2018-09-28 2019-09-27 Polymers, charge transport paints, charge transport films, organic electroluminescent elements TWI837184B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-184283 2018-09-28
JP2018184283 2018-09-28

Publications (2)

Publication Number Publication Date
TW202035367A true TW202035367A (en) 2020-10-01
TWI837184B TWI837184B (en) 2024-04-01

Family

ID=

Also Published As

Publication number Publication date
JPWO2020067288A1 (en) 2021-09-24
CN112789298B (en) 2024-04-30
JP7375765B2 (en) 2023-11-08
CN112789298A (en) 2021-05-11
WO2020067288A1 (en) 2020-04-02
KR20210070309A (en) 2021-06-14

Similar Documents

Publication Publication Date Title
KR101817808B1 (en) Electroactive materials
KR101616149B1 (en) Electroactive materials
TWI808111B (en) Charge-transporting paint, charge-transporting film, and organic electroluminescent device
KR101904510B1 (en) Oligoaniline derivative, charge-transporting varnish, and organic electroluminescent element
JP6947180B2 (en) Varnish for forming charge-transporting thin films
JP6760455B2 (en) Aniline derivative and its manufacturing method
JP6678574B2 (en) Charge transporting varnish
JP7375765B2 (en) Polymers and their uses
TWI620732B (en) Electrode transport varnish for metal anode and composite
EP3101002B1 (en) Aryl sulfonic acid compound and use of same
JP2024041937A (en) Charge transporting thin film
KR20160114629A (en) Aryl sulfonic acid compound and use thereof
WO2022209891A1 (en) Polymer and use thereof
TWI837184B (en) Polymers, charge transport paints, charge transport films, organic electroluminescent elements
KR20210144750A (en) Fluorene derivatives and their use
KR20220025814A (en) charge transport varnish
WO2015146912A1 (en) Fluorene derivative and use thereof
JP6503675B2 (en) Charge transporting varnish, charge transporting thin film and organic electroluminescent device
KR102476004B1 (en) Fluorine atom-containing polymer and use thereof